In addition to caspase inhibition, X-linked inhibitor of apoptosis (XIAP) induces NF-{kappa}B and MAP kinase activation during TGF-b and BMP receptor signaling and upon overexpression. Here we show that the BIR1 domain of XIAP, which has no previously ascribed function, directly interacts with TAB1 to induce NF-{kappa}B activation. TAB1 is an upstream adaptor for the activation of the kinase TAK1, which in turn couples to the NF-{kappa}B pathway. We report the crystal structures of BIR1, TAB1, and the BIR1/TAB1 complex. The BIR1/TAB1 structure reveals a striking butterfly-shaped dimer and the detailed interaction between BIR1 and TAB1. Structure-based mutagenesis and knockdown of TAB1 show unambiguously that the BIR1/TAB1 interaction is crucial for XIAP-induced TAK1 and NF-{kappa}B activation. We show that although not interacting with BIR1, Smac, the antagonist for caspase inhibition by XIAP, also inhibits the XIAP/TAB1 interaction. Disruption of BIR1 dimerization abolishes XIAP-mediated NF-{kappa}B activation, implicating a proximity-induced mechanism for TAK1 activation.

X-linked inhibitor of apoptosis (XIAP) is a potent negative regulator of apoptosis. It also plays a role in BMP signaling, TGF-{beta} signaling, and copper homeostasis. Previous structural studies have shown that the baculoviral IAP repeat (BIR2 and BIR3) domains of XIAP interact with the IAP-binding-motifs (IBM) in several apoptosis proteins such as Smac and caspase-9 via the conserved IBM-binding groove. Here, we report the crystal structure in two crystal forms of the BIR1 domain of XIAP, which does not possess this IBM-binding groove and cannot interact with Smac or caspase-9. Instead, the BIR1 domain forms a conserved dimer through the region corresponding to the IBM-binding groove. Structural and sequence analyses suggest that this dimerization of BIR1 in XIAP may be conserved in other IAP family members such as cIAP1 and cIAP2 and may be important for the action of XIAP in TGF-{beta} and BMP signaling and the action of cIAP1 and cIAP2 in TNF receptor signaling.

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codesand corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

The effect of antisymmetric CĖH stretching excitation of CH{sub 4} on the dynamics and reactivity of the O({sup 1}D) + CH{sub 4} ? OH + CD{sub 3} reaction at the collision energy of 6.10 kcal/mol has been investigated using the crossed-beam and time-sliced velocity map imaging techniques. The antisymmetric CĖH stretching mode excited CH{sub 4} molecule was prepared by direct infrared excitation. From the measured images of the CH{sub 3} products with the infrared laser on and off, the product translational energy and angular distributions were derived for both the ground and vibrationally excited reactions. Experimental results show that the vibrational energy of the antisymmetric stretching excited CH{sub 4} reagent is channeled exclusively into the vibrational energy of the OH co-products and, hence, the OH products from the excited-state reaction are about one vibrational quantum hotter than those from the ground-state reaction, and the product angular distributions are barely affected by the vibrational excitation of the CH{sub 4} reagent. The reactivity was found to be suppressed by the antisymmetric stretching excitation of CH{sub 4} for all observed CH{sub 3} vibrational states. The degree of suppression is different for different CH{sub 3} vibrational states: the suppression is about 40%Ė60% for the ground state and the umbrella mode excited CH{sub 3} products, while for the CH{sub 3} products with one quantum symmetric stretching mode excitation, the suppression is much less pronounced. In consequence, the vibrational state distribution of the CH{sub 3} product from the excited-state reaction is considerably different from that of the ground-state reaction.

CH2M HILL Plateau Remediation Company CH2M HILL Plateau Remediation Company The Office of Hea1th, Safety and Security's Office of Enforcement and Oversight has evaluated the facts and circumstances of a series of radiological work deficiencies at the Plutonium Finishing Plant (PFP) and the 105 K-East Reactor Facility (105KE Reactor) by CH2M HILL Plateau Remediation Company (CHPRC). The radiological work deficiencies at PFP are documented in the April 29, 2011, Department of Energy Richland

Here, we report calculations of the electronic structure, vibrational properties, and transport for the p-type semiconductors, SrAgChF (Ch = S, Se, and Te). We find soft phonons with low frequency optical branches intersecting the acoustic modes below 50 cm‚Äď1, indicative of a material with low thermal conductivity. The bands at and near the valence-band maxima are highly two-dimensional, which leads to high thermopowers even at high carrier concentrations, which is a combination that suggests good thermoelectric performance. These materials may be regarded as bulk realizations of superlattice thermoelectrics.

SAPO-34 membranes were synthesized by several routes towards N-2/CH4 separation. Membrane synthesis parameters including water content in the gel, crystallization time, support pore size, and aluminum source were investigated. High performance N-2-selective membranes were obtained on 100-nm-pore alumina tubes by using Al(i-C3H7O)(3) as aluminum source with a crystallization time of 6 h. These membranes separated N-2 from CH, with N-2 permeance as high as 500 GPU with separation selectivity of 8 at 24 degrees C. for a 50/50 N-2/CH4 mixture. Nitrogen and CH, adsorption isotherms were measured on SAPO-34 crystals. The N-2 and CH, heats of adsorption were 11 and 15 kJ/mol, respectively, which lead to a preferential adsorption of CE-H-4 over N-2 in the N-2/CH4 mixture. Despite this, the SAPO-34 membranes were selective for N-2 over CH4 in the mixture because N-2 diffuses much faster than CH4 and differences in diffusivity played a more critical role than the competitive adsorption. Preliminary economic evaluation indicates that the required N-2/CH4 selectivity would be 15 in order to maintain a CH4 loss below 10%. For small nitrogen-contaminated gas wells, our current SAPO-34 membranes have potential to compete with the benchmark technology cryogenic distillation for N-2 rejection. (C) 2015 Elsevier B.V. All rights reserved,

The Chequamegon Ecosystem-Atmosphere Study (ChEAS) is a multi-organizational research effort studying biosphere/atmosphere interactions within a northern mixed forest in Northern Wisconsin. A primary goal is to understand the processes controlling forest-atmosphere exchange of carbon dioxide and the response of these processes to climate change. Another primary goal is to bridge the gap between canopy-scale flux measurements and the global CO2 flask sampling network. The ChEAS flux towers participate in AmeriFlux, and the region is an EOS-validation site. The WLEF tower is a NOAA-CMDL CO2 sampling site. ChEAS sites are primarily located within or near the Chequamegon-Nicolet National Forest in northern Wisconsin, with one site in the Ottawa National Forest in the upper peninsula of Michigan. Current studies observe forest/atmosphere exchange of carbon dioxide at canopy and regional scales, forest floor respiration, photosynthesis and transpiration at the leaf level and use models to scale to canopy and regional levels. EOS-validation studies quantitatively assess the land cover of the area using remote sensing and conduct extensive ground truthing of new remote sensing data (i.e. ASTER and MODIS). Atmospheric remote sensing work is aimed at understanding atmospheric boundary layer dynamics, the role of entrainment in regulating the carbon dioxide mixing ratio profiles through the lower troposphere, and feedback between boundary layer dynamics and vegetation (especially via the hydrologic cycle). Airborne studies have included include balloon, kite and aircraft observations of the CO2 profile in the troposphere.

This SBIR project evaluated the potential to remediate geologic CO2 sequestration sites into useful methane gas fields by application of methanogenic bacteria. Such methanogens are present in a wide variety of natural environments, converting CO2 into CH4 under natural conditions. We conclude that the process is generally feasible to apply within many of the proposed CO2 storage reservoir settings. However, extensive further basic R&D still is needed to define the precise species, environments, nutrient growth accelerants, and economics of the methanogenic process. Consequently, the study team does not recommend Phase III commercial application of the technology at this early phase.

CH2M-WG Idaho, LLC - WCO-2011-01 Consent Order, CH2M-WG Idaho, LLC - WCO-2011-01 October 6, 2011 Issued to CH2M-WG Idaho, LLC related to a Hoisting Incident that occurred at the Sodium Bearing Waste Treatment Project at the Idaho National Laboratory On October 6, 2011, the U.S. Department of Energy (DOE) Office of Health Safety and Security's Office of Enforcement and Oversight issued a Consent Order to CH2M-WG Idaho, LLC (CWI) for deficiencies in CWI's oversight of its construction

This WIPP Bin-Scale CH TRU Waste Test program described herein will provide relevant composition and kinetic rate data on gas generation and consumption resulting from TRU waste degradation, as impacted by synergistic interactions due to multiple degradation modes, waste form preparation, long-term repository environmental effects, engineered barrier materials, and, possibly, engineered modifications to be developed. Similar data on waste-brine leachate compositions and potentially hazardous volatile organic compounds released by the wastes will also be provided. The quantitative data output from these tests and associated technical expertise are required by the WIPP Performance Assessment (PA) program studies, and for the scientific benefit of the overall WIPP project. This Test Plan describes the necessary scientific and technical aspects, justifications, and rational for successfully initiating and conducting the WIPP Bin-Scale CH TRU Waste Test program. This Test Plan is the controlling scientific design definition and overall requirements document for this WIPP in situ test, as defined by Sandia National Laboratories (SNL), scientific advisor to the US Department of Energy, WIPP Project Office (DOE/WPO). 55 refs., 16 figs., 19 tabs.

On the basis of SCF and single reference MP2 calculations, the full potential energy surface of the interaction between CH{sub 4} and CN{sup {minus}} was studied using extended basis sets of up to near Hartree-Fock limit quality. Colinear arrangements C-N{sup {minus}}{hor_ellipsis}H-CH{sub 3} and N-C{sup {minus}}{hor_ellipsis}H-CH{sub 3} are found to be the only two energy minima. The binding energies of these two structures are calculated to be 2.5 and 2.1 kcal/mol, respectively, at the MP2 level. The full vibrational analyses of two structures show a red shift of about 30 cm{sup {minus}1} for the v{sub s} C-H stretching.

Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH{sub 3}CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO{sub 2} radicals by reaction with O{sub 2}. The CH{sub 3} radical yield has been determined using the same technique following their conversion into CH{sub 3}O{sub 2}. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO{sub 2} profiles, obtained under various O{sub 2} concentrations, to a complex model, while the CH{sub 3} yield has been determined relative to the CH{sub 3} yield from 248 nm photolysis of CH{sub 3}I. Time resolved HO{sub 2} profiles under very low O{sub 2} concentrations suggest that another unknown HO{sub 2} forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O{sub 2}. HO{sub 2} profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH{sub 3}CHO?+?h?{sub 248nm} ? CH{sub 3}CHO{sup *}, CH{sub 3}CHO{sup *} ? CH{sub 3}?+?HCO??{sub 1a} = 0.125?Ī?0.03, CH{sub 3}CHO{sup *} ? CH{sub 3}?+?H?+?CO??{sub 1e} = 0.205?Ī?0.04, CH{sub 3}CHO{sup *}?{sup o{sub 2}}CH{sub 3}CO?+?HO{sub 2}??{sub 1f} = 0.07?Ī?0.01. The CH{sub 3}O{sub 2} quantum yield has been determined in separate experiments as ?{sub CH{sub 3}} = 0.33 Ī 0.03 and is in excellent agreement with the CH{sub 3} yields derived from the HO{sub 2} measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH{sub 3}CHO. From arithmetic considerations taking into account the HO{sub 2} and CH{sub 3} measurements we deduce a remaining quantum yield for the molecular pathway: CH{sub 3}CHO{sup *} ? CH{sub 4}?+?CO??{sub 1b} = 0.6. All experiments can be consistently explained with absence of the formerly considered

(CH.sub.3).sub.3 SiNSO is produced by the reaction of ((CH.sub.3).sub.3 Si).sub.2 NH with SO.sub.2. Also produced in the reaction are ((CH.sub.3).sub.3 Si).sub.2 O and a new solid compound [NH.sub.4 ][(CH.sub.3).sub.3 SiOSO.sub.2 ]. Both (CH.sub.3).sub.3 SiNSO and [NH.sub.4 ][(CH.sub.3).sub.3 SiOSO.sub.2 ] have fluorescent properties. The reaction of the subject invention is used in a method of measuring the concentration of SO.sub.2 pollutants in gases. By the method, a sample of gas is bubbled through a solution of ((CH.sub.3).sub.3 Si).sub.2 NH, whereby any SO.sub.2 present in the gas will react to produce the two fluorescent products. The measured fluorescence of these products can then be used to calculate the concentration of SO.sub.2 in the original gas sample. The solid product [NH.sub.4 ][(CH.sub.3).sub.3 SiOSO.sub.2 ] may be used as a standard in solid state NMR spectroscopy.

Contract at its Hanford Site | Department of Energy CH2M Hill Plateau Remediation Company for Plateau Remediation Contract at its Hanford Site DOE Selects CH2M Hill Plateau Remediation Company for Plateau Remediation Contract at its Hanford Site June 19, 2008 - 1:29pm Addthis WASHINGTON, DC - The U.S. Department of Energy (DOE) today announced that CH2M Hill Plateau Remediation Company has been selected as the plateau remediation contractor for DOE's Hanford Site in southeastern Washington

Complex ChIMES: "Limited only by ... ChIMES: "Limited only by our imaginations" Posted: March 26, 2015 - 4:18pm The ChIMES team's investigators each brought unique expertise to the project. A three-year collaboration of scientists from Y-12 National Security Complex and The University of Tennessee, Knoxville, resulted in the innovation of a patented chemical sensor that is unique in several aspects: it's inexpensive, tiny and portable; it promises virtually limitless

CH2M HILL Plateau Remediation Company CH2M HILL Plateau Remediation Company The Office of Hea1th, Safety and Security's Office of Enforcement and Oversight has evaluated the facts and circumstances of a series of radiological work deficiencies at the Plutonium Finishing Plant (PFP) and the 105 K-East Reactor Facility (105KE Reactor) by CH2M HILL Plateau Remediation Company (CHPRC). The radiological work deficiencies at PFP are documented in the April 29, 2011, Department of Energy Richland

April 2015 | Department of Energy URS | CH2M Oak Ridge LLC - April 2015 Voluntary Protection Program Onsite Review, URS | CH2M Oak Ridge LLC - April 2015 April 2015 UCOR is admitted to the Department of Energy Voluntary Protection Program as a Star Participant. This report summarizes the results from the evaluation of URS | CH2M OAK RIDGE LLC (UCOR) in Oak Ridge, Tennessee during the period of April 14-23 2015, and provides the Associate Under Secretary for AU with the necessary information

Issued to CH2M-Washington Group Idaho, LLC, related to Radiation Protection Program Deficiencies at the Radioactive Waste Management Complex - Accelerated Retrieval Project at the Idaho National Laboratory

Here, we report calculations of the electronic structure, vibrational properties, and transport for the p-type semiconductors, SrAgChF (Ch = S, Se, and Te). We find soft phonons with low frequency optical branches intersecting the acoustic modes below 50 cm‚Äď1, indicative of a material with low thermal conductivity. The bands at and near the valence-band maxima are highly two-dimensional, which leads to high thermopowers even at high carrier concentrations, which is a combination that suggests good thermoelectric performance. These materials may be regarded as bulk realizations of superlattice thermoelectrics.

Atmospheric pressure of helium (He) and methane (CH{sub 4}) mixture discharge characteristics are investigated using emission spectroscopic methods. Plasmas are produced in a radio frequency capacitively coupled device at atmospheric pressure in the ambient air. Without the CH{sub 4} gas introduced in the plasma, the emission spectrum exhibits typical helium discharge characteristics showing helium atomic lines with nitrogen molecular bands and oxygen atomic lines resulting from air impurities. Addition of a small amount (<1%) of CH{sub 4} to the supplied He results in the emission of CN (B{sup 2}{sigma}{sup +}-X{sup 2}{sigma}{sup +}: violet system) and CH (A{sup 2}{delta}-X{sup 2} product : 430 nm system) molecular bands. Analyzing the CN and CH diatomic molecular emission spectra, the vibrational temperature (T{sub vib}) and rotational temperature (T{sub rot}) are simultaneously obtained. As input power levels are raised from 20 W to 200 W, T{sub vib} and T{sub rot} are increased from 4230 K to 6310 K and from 340 K to 500 K, respectively. On the contrary, increasing the CH{sub 4} amount brings about the decrease of both temperatures because CH{sub 4} is harder to ionize than He. The emission intensities of CN and CH radicals, which are important in plasma processing, are also changed along with the temperature variation. From the results, the atmospheric pressure plasma shows strong nonequilibrium discharge properties, which may be effectively utilized for thermal damage free material treatments.

The quaternary rare-earth chalcogenides RE{sub 3}CuGaS{sub 7} and RE{sub 3}CuGaSe{sub 7} (RE=La‚ÄďNd) have been prepared by reactions of the elements at 1050 ¬įC and 900 ¬įC, respectively. They crystallize in the noncentrosymmetric La{sub 3}CuSiS{sub 7}-type structure (hexagonal, space group P6{sub 3}, Z=2) in which the a-parameter is largely controlled by the RE component (a=10.0‚Äď10.3 √Ö for the sulfides and 10.3‚Äď10.6 √Ö for the selenides) whereas the c-parameter is essentially fixed by the choice of Ga and chalcogen atoms within tetrahedral units (c=6.1 √Ö for the sulfides and 6.4 √Ö for the selenides). They extend the series RE{sub 3}MGaCh{sub 7}, previously known for divalent metal atoms (M=Mn‚ÄďNi), differing in that the Cu atoms in RE{sub 3}CuGaCh{sub 7} occupy trigonal planar sites instead of octahedral sites. Among quaternary chalcogenides RE{sub 3}MM‚Ä≤Ch{sub 7}, the combination of monovalent (M=Cu) and trivalent (M‚Ä≤=Ga) metals is unusual because it appears to violate the condition of charge balance satisfied by most La{sub 3}CuSiS{sub 7}-type compounds. The possibility of divalent Cu atoms was ruled out by bond valence sum analysis, magnetic measurements, and X-ray photoelectron spectroscopy. The electron deficiency in RE{sub 3}CuGaCh{sub 7} is accommodated through S-based holes at the top of the valence band, as shown by band structure calculations on La{sub 3}CuGaS{sub 7}. An optical band gap of about 2.0 eV was found for La{sub 3}CuGaSe{sub 7}. - Graphical abstract: The chalcogenides RE{sub 3}CuGaCh{sub 7} contain monovalent Cu in trigonal planes and trivalent Ga in tetrahedra; they are electron-deficient representatives of La{sub 3}CuSiS{sub 7}-type compounds, which normally satisfy charge balance. - Highlights: ‚ÄĘ Quaternary chalcogenides RE{sub 3}CuGaCh{sub 7} (RE=La‚ÄďNd; Ch=S, Se) were prepared. ‚ÄĘ Bond valence sums, magnetism, and XPS data give evidence for monovalent Cu. ‚ÄĘ Crystal structures reveal high anisotropy of Cu displacement. ‚

By means of time-resolved Fourier transform infrared absorption spectroscopy, we have investigated the 193 nm photodissociation and photoisomerization dynamics of the prototype molecule of {alpha},{beta}-enones, acrolein (CH{sub 2}=CHCHO) in CH{sub 3}CN solution. The primary photolysis channels and absolute branching ratios are determined. The most probable reaction mechanisms are clarified by control experiments monitoring the product yields varied with the triplet quencher addition. The predominant channel is the 1,3-H migration yielding the rearrangement product CH{sub 3}CH=C=O with a branching ratio of 0.78 and the less important channel is the {alpha} cleavage of C-H bond yielding radical fragments CH{sub 2}=CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet {sup 3}({pi}{pi}{sup *}) state rather than the ground S{sub 0} state and the {alpha} cleavage of C-H bond is more likely to proceed in the singlet S{sub 1} {sup 1}(n{pi}{sup *}) state. From the solution experiments we have not only acquired clues clarifying the previous controversial mechanisms, but also explored different photochemistry in solution. Compared to the gas phase photolysis which is dominated by photodissociation channels, the most important channel in solution is the photoisomerization of 1,3-H migration. The reason leading to the different photochemistry in solution is further ascribed to the solvent cage effect.

The exchange of carbon dioxide for methane in natural gas hydrates is an attractive approach to harvesting CH4 for energy production while simultaneously sequestering CO2. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH4)1-x(CO2)x¬∑5.75H2O provides a model system to study how the distinct bonding and shapes of CH4 and CO2 influence the structure and properties of the compound. In this paper, high-resolution neutron diffraction was used to examine mixed CO2/CH4 gas hydrates. CO2-rich hydrates had smaller lattice parameters, which were attributed to the higher affinity of the CO2 molecule interacting with H2O molecules thatmore¬†¬Ľ form the surrounding cages, and resulted in a reduction in the unit-cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. Finally, these results provide important insights on the impact and mechanisms for the structure of mixed CH4/CO2 gas hydrate.¬ę¬†less

Acetonitrile (CH3CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C‚Č°N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. In this study, it is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH¬∑¬∑¬∑N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp2 and sp3more¬†¬Ľ bonded carbon. Lastly, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.¬ę¬†less

The exchange of CO2 for CH4 in natural gas hydrates is an attractive approach to methane for energy production while simultaneously sequestering CO2. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH4)1-x(CO2)x 5.75H2O provides a model system to study how the distinct bonding and shapes of CH4 and CO2 influence the structure and properties of the compound. High-resolution neutron diffraction was used to examine mixed CO2/CH4 gas hydrates. CO2-rich hydrates had smaller lattice parameters, which were attributed to the higher affinity of the CO2 molecule interacting with H2O molecules that form the surrounding cages, and resulted in a reduction in the unit cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. These results provide important insights on the impact and mechanisms for exchanging CH4 and CO2.

CH{sub 3}NH{sub 3}I, PbI{sub 2} and CH{sub 3}NH{sub 3}PbI{sub 3} films were fabricated by evaporation and characterized with X-ray Photoelectron Spectroscopy (XPS) and X-ray diffraction (XRD). The XPS results indicate that the PbI{sub 2} and CH{sub 3}NH{sub 3}PbI{sub 3} films are more uniform and stable than the CH{sub 3}NH{sub 3}I film. The atomic ratio of the CH{sub 3}NH{sub 3}I, PbI{sub 2} and CH{sub 3}NH{sub 3}PbI{sub 3} films are C:N:I=1.00:1.01:0.70, Pb:I= 1.00:1.91 and C: N: Pb: I = 1.29:1.07:1.00:2.94, respectively. The atomic ratio of CH{sub 3}NH{sub 3}PbI{sub 3} is very close to that of the ideal perovskite. Small angle x-ray diffraction results demonstrate that the as evaporated CH{sub 3}NH{sub 3}PbI{sub 3} film is crystalline. The valence band maximum (VBM) and work function (WF) of the CH{sub 3}NH{sub 3}PbI{sub 3} film are about 0.85eV and 4.86eV, respectively.

The photodissociation of carbon compounds by solar UV radiation at a heliocentric distance of 1 AU is examined, comparing published observational data with the predictions of theoretical models and results from laboratory experiments. It is shown that species other than CO, including CN, CH, CH(+), C2, and C3, can contribute to the observed brightness of the VUV lines of C I (156.1, 165.7, and 193.1 nm) and C II (133.5 nm) in comet comae. CN photodissociation is also found to produce metastable 2D0 and 2P0 N I atoms, possibly leading (at heliocentric distances less than 0.25 AU) to 143.9-nm emission via resonance fluorescence. 37 refs.

The reactions of the methylidyne radical (CH) with ethylene, acetylene, allene, and methylacetylene are studied at room temperature using tunable vacuum ultraviolet (VUV) photoionization and time-resolved mass spectrometry. The CH radicals are prepared by 248 nm multiphoton photolysis of CHBr3 at 298 K and react with the selected hydrocarbon in a helium gas flow. Analysis of photoionization efficiency versus VUV photon wavelength permits isomer-specific detection of the reaction products and allows estimation of the reaction product branching ratios. The reactions proceed by either CH insertion or addition followed by H atom elimination from the intermediate adduct. In the CH + C2H4 reaction the C3H5 intermediate decays by H atom loss to yield 70(+-8)percent allene, 30(+-8)percent methylacetylene and less than 10percent cyclopropene, in agreement with previous RRKM results. In the CH + acetylene reaction, detection of mainly the cyclic C3H2 isomer is contrary to a previous RRKM calculation that predicted linear triplet propargylene to be 90percent of the total H-atom co-products. High-level CBS-APNO quantum calculations and RRKM calculation for the CH + C2H2 reaction presented in this manuscript predict a higher contribution of the cyclic C3H2 (27.0percent) versus triplet propargylene (63.5percent) than these earlier predictions. Extensive calculations on the C3H3 and C3H2D system combined with experimental isotope ratios for the CD + C2H2 reaction indicate that H-atom assisted isomerization in the present experiments is responsible for the discrepancy between the RRKM calculations and the experimental results. Cyclic isomers are also found to represent 30(+-6)percent of the detected products in the case of CH + methylacetylene, together with 33(+-6)percent 1,2,3-butatriene and 37(+-6)percent vinylacetylene. The CH + allene reaction gives 23(+-5)percent 1,2,3-butatriene and 77(+-5)percent vinylacetylene, whereas cyclic isomers are produced below the detection limit

In 2006, California passed the landmark assembly bill AB-32 to reduce California's emissions of greenhouse gases (GHGs) that contribute to global climate change. AB-32 commits California to reduce total GHG emissions to 1990 levels by 2020, a reduction of 25 percent from current levels. To verify that GHG emission reductions are actually taking place, it will be necessary to measure emissions. We describe atmospheric inverse model estimates of GHG emissions obtained from the California Greenhouse Gas Emissions Measurement (CALGEM) project. In collaboration with NOAA, we are measuring the dominant long-lived GHGs at two tall-towers in central California. Here, we present estimates of CH{sub 4} emissions obtained by statistical comparison of measured and predicted atmospheric mixing ratios. The predicted mixing ratios are calculated using spatially resolved a priori CH{sub 4} emissions and surface footprints, that provide a proportional relationship between the surface emissions and the mixing ratio signal at tower locations. The footprints are computed using the Weather Research and Forecast (WRF) coupled to the Stochastic Time-Inverted Lagrangian Transport (STILT) model. Integral to the inverse estimates, we perform a quantitative analysis of errors in atmospheric transport and other factors to provide quantitative uncertainties in estimated emissions. Regressions of modeled and measured mixing ratios suggest that total CH{sub 4} emissions are within 25% of the inventory estimates. A Bayesian source sector analysis obtains posterior scaling factors for CH{sub 4} emissions, indicating that emissions from several of the sources (e.g., landfills, natural gas use, petroleum production, crops, and wetlands) are roughly consistent with inventory estimates, but livestock emissions are significantly higher than the inventory. A Bayesian 'region' analysis is used to identify spatial variations in CH{sub 4} emissions from 13 sub-regions within California. Although, only

Department of Energy M-Washington Group Idaho for Price-Anderson Violations DOE Cites CH2M-Washington Group Idaho for Price-Anderson Violations June 14, 2007 - 1:40pm Addthis WASHINGTON, DC - The U.S. Department of Energy (DOE) today notified CH2M-Washington Group Idaho (CWI) that it will fine the company $55,000 for violations of the Department's nuclear safety requirements. CWI is the prime contractor responsible for managing the Idaho Cleanup Project at the Idaho National Laboratory site.

Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Wednesday, 28 June 2006 00:00 Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store

Proof-of-principle measurements of the electron densities, temperatures, and ionization states of spherically compressed multi-shocked CH (polystyrene) capsules have been achieved using spectrally resolved x-ray Thomson scattering. A total energy of 13.5 kJ incident on target is used to compress a 70 őľm thick CH shell above solid-mass density using three coalescing shocks. Separately, a laser-produced zinc He-őĪ x-ray source at 9 keV delayed 200 ps-800 ps after maximum compression is used to probe the plasma in the non-collective scattering regime. The data show that x-ray Thomson scattering enables a complete description of the time-dependent hydrodynamic evolution of shock-compressed CH capsules,more¬†¬Ľ with a maximum measured density of ŌĀ > 6 g cm‚Äď3. Additionally, the results demonstrate that accurate measurements of x-ray scattering from bound-free transitions in the CH plasma demonstrate strong evidence that continuum lowering is the primary ionization mechanism of carbon L-shell electrons.¬ę¬†less

High resolution planar laser-induced fluorescence (PLIF) was applied to investigate the local flame front structures of turbulent premixed methane/air jet flames in order to reveal details about turbulence and flame interaction. The targeted turbulent flames were generated on a specially designed coaxial jet burner, in which low speed stoichiometric gas mixture was fed through the outer large tube to provide a laminar pilot flame for stabilization of the high speed jet flame issued through the small inner tube. By varying the inner tube flow speed and keeping the mixture composition as that of the outer tube, different flames were obtained covering both the laminar and turbulent flame regimes with different turbulent intensities. Simultaneous CH/CH{sub 2}O, and also OH PLIF images were recorded to characterize the influence of turbulence eddies on the reaction zone structure, with a spatial resolution of about 40 {mu}m and temporal resolution of around 10 ns. Under all experimental conditions, the CH radicals were found to exist only in a thin layer; the CH{sub 2}O were found in the inner flame whereas the OH radicals were seen in the outer flame with the thin CH layer separating the OH and CH{sub 2}O layers. The outer OH layer is thick and it corresponds to the oxidation zone and post-flame zone; the CH{sub 2}O layer is thin in laminar flows; it becomes broad at high speed turbulent flow conditions. This phenomenon was analyzed using chemical kinetic calculations and eddy/flame interaction theory. It appears that under high turbulence intensity conditions, the small eddies in the preheat zone can transport species such as CH{sub 2}O from the reaction zones to the preheat zone. The CH{sub 2}O species are not consumed in the preheat zone due to the absence of H, O, and OH radicals by which CH{sub 2}O is to be oxidized. The CH radicals cannot exist in the preheat zone due to the rapid reactions of this species with O{sub 2} and CO{sub 2} in the inner-layer of the

Microwave (MW), millimeter-wave (MMW) and Fourier-transform far-infrared (FTFIR) transitions in the first two torsional states (v{sub t} = 0 below the barrier and v{sub t} = 1 straddling the barrier) of the ground vibrational state of C-13 methanol have been globally treated and successfully fitted to within assigned measurement uncertainties using a program (I. Kleiner and M. Godefroid private communication) originally designed for acetaldehyde (CH{sub 3}CHO) based on the formalism of Herbst et al. The {sup 13}CH{sub 3}OH data set (v {sub t} {le} 1, J {le} 20, K{sub max} {le} 14) contains 725 MW and MMW lines, assigned a {+-}50 kHz measurement uncertainty apart from a few K-doublet lines, and 6283 FTFIR lines each assigned an uncertainty of {+-}0.0002 cm{sup -1} = {+-}6 MHz. A very satisfactory convergent fit has been achieved using 55 adjustable and 2 fixed parameters, yielding an overall weighted standard deviation of 0.962. Calculations employing the parameters from the final fit reveal possible C-13 assignments for 28 lines appearing in natural abundance in the newly-measured methanol microwave atlas from 7 to 200 GHz compiled by the group of K. Takagi at Toyama University.

Following photodissociation of acetaldehyde (CH{sub 3}CHO) at 308 nm, the CO(v = 1‚Äď4) fragment is acquired using time-resolved Fourier-transform infrared emission spectroscopy. The CO(v = 1) rotational distribution shows a bimodal feature; the low- and high-J components result from H-roaming around CH{sub 3}CO core and CH{sub 3}-roaming around CHO radical, respectively, in consistency with a recent assignment by Kable and co-workers (Lee et al., Chem. Sci. 5, 4633 (2014)). The H-roaming pathway disappears at the CO(v ‚Č• 2) states, because of insufficient available energy following bond-breaking of H + CH{sub 3}CO. By analyzing the CH{sub 4} emission spectrum, we obtained a bimodal vibrational distribution; the low-energy component is ascribed to the transition state (TS) pathway, consistent with prediction by quasiclassical trajectory calculations, while the high-energy component results from H- and CH{sub 3}-roamings. A branching fraction of H-roaming/CH{sub 3}-roaming/TS contribution is evaluated to be (8% ¬Ī 3%)/(68% ¬Ī 10%)/(25% ¬Ī 5%), in which the TS pathway was observed for the first time. The three pathways proceed concomitantly along the electronic ground state surface.

This dataset consists of field measurements of CO2 and CH4 flux, as well as soil properties made during 2013 in Areas A-D of Intensive Site 1 at the Next-Generation Ecosystem Experiments (NGEE) Arctic site near Barrow, Alaska. Included are i) measurements of CO2 and CH4 flux made from June to September (ii) Calculation of corresponding Gross Primary Productivity (GPP) and CH4 exchange (transparent minus opaque) between atmosphere and the ecosystem (ii) Measurements of Los Gatos Research (LGR) chamber air temperature made from June to September (ii) measurements of surface layer depth, type of surface layer, soil temperature and soil moisture from June to September.

This dataset consists of field measurements of CO2 and CH4 flux, as well as soil properties made during 2013 in Areas A-D of Intensive Site 1 at the Next-Generation Ecosystem Experiments (NGEE) Arctic site near Barrow, Alaska. Included are i) measurements of CO2 and CH4 flux made from June to September (ii) Calculation of corresponding Gross Primary Productivity (GPP) and CH4 exchange (transparent minus opaque) between atmosphere and the ecosystem (ii) Measurements of Los Gatos Research (LGR) chamber air temperature made from June to September (ii) measurements of surface layer depth, type of surface layer, soil temperature and soil moisture from June to September.

Protonated methane (CH{sub 5}{sup +}) is thought to be a highly abundant molecular ion in interstellar medium, as well as a potentially bright őľwave- mm wave emitter that could serve as a tracer for methane. This paper describes progress and first successful efforts to obtain a high resolution, supersonically cooled spectrum of CH{sub 5}{sup +} in the 2900-3100 cm{sup ‚ąí1} region, formed in a slit supersonic discharge at low jet temperatures and with sub-Doppler resolution. Short term precision in frequency measurement (< 5 MHz on an hour time scale) is obtained from a thermally controlled optical transfer cavity servoloop locked onto a frequency stabilized HeNe laser. Long term precision (< 20 MHz day-to-day) due to pressure, temperature and humidity dependent index of refraction effects in the optical transfer cavity is also present and discussed.

6 . The U.S. Department of Energy and contractor CH2M HILL Plateau Remediation Company manage the Waste Encapsulation and Storage Facility at the Hanford Site in southeast Washington state. Waste Encapsulation and Storage Facility Background The Waste Encapsulation and Storage Facility (WESF) provides safe and compliant underwater storage for 1,936 highly radioactive capsules containing the elements cesium and strontium. In the 1970s, radioactive isotopes of the chemical elements cesium and

The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

2 10 CFR Ch. III (1-1-11 Edition) Pt. 851, App. B must meet the applicable electrical safety codes and standards referenced in ¬ß 851.23. 11. NANOTECHNOLOGY SAFETY-RESERVED The Department has chosen to reserve this section since policy and procedures for nano- technology safety are currently being devel- oped. Once these policies and procedures have been approved, the rule will be amended to include them through a rulemaking con- sistent with the Administrative Procedure Act. 12. WORKPLACE

This paper addresses the underlying problems involved in developing institution-wide QA programs at DOE funded basic research facilities, and suggests concrete ways in which QA professionals and basic researchers can find common ground in describing and analyzing those activities to the satisfaction of both communities. The paper is designed to be a springboard into workshop discussions which can define a path for developing institution-wide QA programs based on the experience gained with DOE-CH and Fermilab.

The velocity and angular distributions of O {sup 1}D photofragments arising from UV excitation of the CH{sub 2}OO intermediate on the B {sup 1}A??X {sup 1}A? transition are characterized using velocity map ion imaging. The anisotropic angular distribution yields the orientation of the transition dipole moment, which reflects the ?*?? character of the electronic transition associated with the COO group. The total kinetic energy release distributions obtained at several photolysis wavelengths provide detail on the internal energy distribution of the formaldehyde cofragments and the dissociation energy of CH{sub 2}OO X {sup 1}A? to O {sup 1}D + H{sub 2}CO X {sup 1}A{sub 1}. A common termination of the total kinetic energy distributions, after accounting for the different excitation energies, gives an upper limit for the CH{sub 2}OO X {sup 1}A? dissociation energy of D{sub 0}? 54 kcal mol{sup ?1}, which is compared with theoretical predictions including high level multi-reference ab initio calculations.

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v3 and 2v3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v1 symmetric stretch of CH4 is more effective at promoting the dissociative chemisorption of CH4 than exciting the 1v3 antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabaticmore¬†¬Ľ states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.¬ę¬†less

Catalytic oxidative CĖH acetoxylation of 8-methylquinoline as a model substrate with O2 as oxidant was performed using palladium(II) carboxylate catalysts derived from four different pyridinecarboxylic acids able to form palladium(II) chelates of different size. A comparison of the rates of the substrate CĖH activation and the O2 activation steps shows that the CĖH activation step is rate-limiting, whereas the O2 activation occurs at a much faster rate already at 20 įC. The chelate ring size and the chelate ring strain of the catalytically active species are proposed to be the key factors affecting the rate of the CĖH activation.

0 11.0 Response Response to to P P ublic ublic Comment Comment 11-1 DOE/EIS-0287 11.1 Introduction This chapter provides responses from the U.S. Department of Energy (DOE) and the State of Idaho to public comments on the Draft Idaho High-Level Waste and Facilities Disposition Environmental Impact Statement (HLW & FD EIS) and identifies where those public comments led to changes to the EIS. The State of Idaho, a cooperating agency in the preparation of the EIS, participated in the process of

.0 12.0 Distribution Distribution List List - New Information - 12-1 DOE/EIS-0287 The U.S. Department of Energy (DOE) pro- vided copies of this Final Environmental Impact Statement (EIS) to Federal, state, and local elected and appointed officials and agencies of government; Native American groups; national, state, and local environmental and public interest groups; and other organizations and individuals list- ed below. In addition, DOE sent copies of the Final EIS to all persons who comment-

4 Background 2.1.3 CURRENT MISSION The current INEEL mission is to develop, demonstrate, and deploy advanced engineering technology and systems to improve national competitiveness and security, to make the pro- duction and use of energy more efficient, and to improve the quality of the environment. Areas of primary emphasis at INEEL include waste management and waste minimization, environ- mental engineering and restoration, energy effi- ciency, renewable energy, national security and defense,

0 3.0 Alterna Alterna tiv tiv es es 3-1 DOE/EIS-0287 This chapter describes the alternatives for waste processing and facility disposi- tion analyzed in this environmental impact statement (EIS) as well as alter- natives eliminated from detailed analy- sis. As required by the Council on Environmental Quality (CEQ) regula- tions implementing the National Environmental Policy Act (NEPA), a No Action alternative is also included. This chapter identifies the U.S. Department of Energy's (DOE's)

13 DOE/EIS-0287 Idaho HLW & FD EIS except the pillar and panel tanks) would be full of mixed transuranic waste in approximately 2017. Other facilities depending on the capacity of the Tank Farm for operation eventually would be shut down due to their inability to discharge liquid waste. Under this alternative, DOE would not meet its commitment to cease use of the Tank Farm by 2012 or to make its mixed HLW road ready by 2035. Facilities required for the No Action Alternative include the bin

3-34 Alternatives transuranic waste/SBW. The EIS also presents the impacts for a grout facility (see Project P2001 in Appendix C.6) that could be used to treat the waste generated after 2005. For pur- poses of assessing transportation impacts, DOE assumed the grouted waste would be character- ized as remote-handled transuranic waste and transported to the Waste Isolation Pilot Plant for disposal (see Appendix C.5). 3.2 Facility Disposition Alternatives The waste processing alternatives described

47 DOE/EIS-0287 Idaho HLW & FD EIS has been provided to the public, committed DOE to restoring the existing contaminated groundwater plume outside the INTEC security fence to meet the current drinking water stan- dard of 4 millirem per year. A performance assessment would be developed for each facility or group of facilities under consideration for disposition, to determine which of the three disposition alternatives would be implemented. The performance assessment results would be used to

0 4.0 Aff Aff ected ected E E nvir nvir onment onment 4-1 DOE/EIS-0287 4.1 Introduction This chapter describes the environment of the Idaho National Engineering and Environmental Laboratory (INEEL) and surrounding area that could be affected by the alternatives analyzed in this environ- mental impact statement (EIS). One of the alternatives under consideration, the Minimum INEEL Processing Alternative, would involve treatment of INEEL high- level waste (HLW) at the Hanford Site. Appendix C.8

1998, INEEL contracts paid $1.4 million to the State of Idaho in Idaho sales taxes and an additional $0.9 million in Idaho franchise tax. 4.4 Cultural Resources 4.4.1 CULTURAL RESOURCE MANAGEMENT AND CONSULTATION AT INEEL Cultural resources at INEEL include archaeolog- ical and historic resources, such as prehistoric camp sites and historic buildings and trails, as well as the plants, animals, physical locations, and other features of INEEL environment impor- tant to the culture of the

18 Affected Environment visual range of the Fort Hall Indian Reservation. The Bitterroot, Lemhi, and Lost River mountain ranges are visible to the north and west of INEEL. East Butte and Middle Butte can be seen near the southern boundary, while Circular and Antelope Buttes are visible to the northeast. Smaller volcanic buttes dot the natural landscape of INEEL, providing a striking contrast to the relatively flat ground surface. The viewscape in general consists of terrain dominated by sage-

40 Affected Environment playas 15 to 20 miles northeast of INTEC, where the water infiltrates. The water in Birch Creek and the Little Lost River is diverted in summer months for irriga- tion prior to reaching INEEL. During periods of unusually high precipitation or rapid snow melt, water from Birch Creek and the Little Lost River may enter INEEL from the northwest and infil- trate the ground, recharging the underlying aquifer. 4.8.1.2 Local Drainage INTEC is located on an alluvial plain

58 Affected Environment 4.9.1 PLANT COMMUNITIES AND ASSOCIATIONS INEEL lies within a cool desert ecosystem dom- inated by shrub-steppe vegetation. The area is relatively undisturbed, providing important habi- tat for species native to the region. Vegetation and habitat on INEEL can be grouped into six types: shrub-steppe, juniper woodlands, native grasslands, modified ephemeral playas, lava, and wetland-like areas. Figure 4-16 shows these areas. More than 90 percent of INEEL falls within the

0 5.0 E E nvir nvir onmental onmental Consequences Consequences 5-1 DOE/EIS-0287 5.1 Introduction Chapter 5 describes the potential environ- mental consequences of implementing each of the alternatives described in Chapter 3. This Final EIS analyzes the alternatives in the Draft EIS and provides corrections and updates as needed. In addition, it analyzes the State of Idaho's Preferred Alternative, Direct Vitrification, and a new option of the Non-Separations Alternative, the Steam Reforming

25 DOE/EIS-0287 Idaho HLW & FD EIS 5.3 Facility Disposition Impacts Section 5.3 presents a discussion of potential impacts associated with the disposition of exist- ing HLW management facilities at INEEL and disposition of new facilities that would be built in support of the proposed waste processing alternatives. The discussion includes (1) the potential impacts of short-term actions in dispo- sitioning new and existing HLW management facilities, (2) the potential long-term impacts from the

45 DOE/EIS-0287 Idaho HLW & FD EIS 5.3.4.2 Existing Facilities Associated with High-Level Waste Management The facilities in this group are those that have historically been used at the INTEC to generate, treat, and store HLW. Because of the number of facilities involved, DOE has grouped them in functional groups for purposes of analysis (see Table 3-3). DOE analyzed the HLW tanks and bin sets for closure under all five disposition sce- narios; however, facilities that support the Tank Farm

0 6.0 Sta Sta tutes tutes , , Regula Regula tions tions , , Consulta Consulta tions tions , , and Other and Other Requir Requir ements ements 6-1 DOE/EIS-0287 This chapter discusses the consultations and coordination the U.S. Department of Energy (DOE) has had with various agen- cies during the preparation of this Environmental Impact Statement (EIS). This chapter also analyzes the complex regulatory issues that arise when consider- ing the various alternatives discussed pre- viously. When

0 7.0 Glossar Glossar y y 7-1 DOE/EIS-0287 Terms in this glossary are defined based on the context in which they are to be used in this Environmental Impact Statement (EIS). - New Information - DOE/EIS-0287 7-2 Glossary 100-year flood A flood that occurs, on average, every 100 years (equates to a 1 percent probability of occurring in any given year). 500-year flood A flood that occurs, on average, every 500 years (equates to a 0.2 percent probability of occurring in any given year). accident An

.0 8.0 Contents of Contents of Appendices Appendices 8-1 DOE/EIS-0287 This chapter provides the contents of the appendices supporting this EIS. The appendices contain technical information supporting the analysis in this EIS, and scanned comment response documents received by DOE during the public com- ment period. The appendices are pub- lished separately and are available on request. - New Information - DOE/EIS-0287 8-2 Contents of Appendices TABLE OF CONTENTS Section Appendix A Site

COVER SHEET Responsible Agency: Lead Federal Agency: U.S. Department of Energy (DOE) Cooperating Agency: The State of Idaho Title: Contact: For additional information on this EIS and the tribal, agency and public involvement process con- ducted in conjunction with its preparation, write or call: This Final EIS is composed of a Summary, Chapters 1 through 13, and appendices. Copies of the EIS or appendices may be requested from Richard Kimmel at the address, phone number, or email address shown

Any physical modelling of a circuit-breaker arc therefore requires an understanding of the radiated energy which is taken into account in the form of a net coefficient. The evaluation of the net emission coefficient is performed by the knowledge of the chemical plasma composition and the resolution of the radiative transfer equation. In this paper, the total radiation which escapes from a CH{sub 4}-N{sub 2} plasma is calculated in the temperature range between 5000 and 30000K on the assumption of a local thermodynamic equilibrium and we have studied the nitrogen effect in the hydrocarbon plasmas.

Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

This study presents the final source catalog of the Chandra ACIS Survey of M33 (ChASeM33). With a total exposure time of 1.4 Ms, ChASeM33 covers {approx}70% of the D{sub 25} isophote (R {approx} 4.0 kpc) of M33 and provides the deepest, most complete, and detailed look at a spiral galaxy in X-rays. The source catalog includes 662 sources, reaches a limiting unabsorbed luminosity of {approx}2.4x10{sup 34} erg s{sup -1} in the 0.35-8.0 keV energy band, and contains source positions, source net counts, fluxes and significances in several energy bands, and information on source variability. The analysis challenges posed by ChASeM33 and the techniques adopted to address these challenges are discussed. To constrain the nature of the detected X-ray source, hardness ratios were constructed and spectra were fit for 254 sources, follow-up MMT spectra of 116 sources were acquired, and cross-correlations with previous X-ray catalogs and other multi-wavelength data were generated. Based on this effort, 183 of the 662 ChASeM33 sources could be identified. Finally, the luminosity function (LF) for the detected point sources as well as the one for the X-ray binaries (XRBs) in M33 is presented. The LFs in the soft band (0.5-2.0 keV) and the hard band (2.0-8.0 keV) have a limiting luminosity at the 90% completeness limit of 4.0 x 10{sup 34} erg s{sup -1} and 1.6 x 10{sup 35} erg s{sup -1}(for D = 817 kpc), respectively, which is significantly lower than what was reported by previous XRB population studies in galaxies more distant than M33. The resulting distribution is consistent with a dominant population of high-mass XRBs as would be expected for M33.

Interaction of femtosecond laser pulses with the intensities 10{sup 21}, 10{sup 22‚ÄČ}W/cm{sup 2} with CH plastic foils is studied in the framework of kinetic theory of laser plasma based on the construction of propagators (in classical limit) for electron and ion distribution functions in plasmas. The calculations have been performed for real densities and charges of plasma ions. Protons are accelerated both in the direction of laser pulse (up to 1‚ÄČGeV) and in the opposite direction (more than 5‚ÄČGeV). The mechanisms of forward acceleration are different for various intensities.

;/:4,4 (; . 1.; e octo: ' J : 18, 1976 Ed Jascevsky Safety Division ChIcago Operations Office MIT CONTFACT INFCE"ATION During the discussions on October 8, 1976, you iquired about information relative to work done by MIT as background infomation for survey planning. The enclosed information is parephrased frorc an unpublished history of program work carried out by the Process Eevclopncnt Group of the Dl.ti,si.on of Raw Katerids, I believe this work was done under contract nuder AT(30-1)956.

TH Ii ' HA' R$,kAW CH EM I CAL CO,M i=ANY A December 30, 1955 U. S. Atomic Energy Commission Oak Ridge OperationwOfflce Post Office Box "E" Oak Ridge, Tennessee Attention: Mr. T. Carberry Dear Mr. Carberry: ' ..> In the process of removing 'classified documents from the safes at the Main Office for des$ruction we discovered two sample cylinders of hexafluorlde. If memory serves us right these sample6 were prepared at the request of the Commission and shipped to the Unl- versity of

E Contract Modification No. 133 i PART I SECTION E INSPECTION AND ACCEPTANCE PAGE NO. E.1 - FAR 52.246-9 - INSPECTION OF RESEARCH AND DEVELOPMENT (SHORT FORM) (APR 1984) E-1 E.2 - CERTIFICATION E-1 Contract No. DE-AC02-07CH11358 Section E Contract Modification No.133 E-1 PART I SECTION E - INSPECTION AND ACCEPTANCE E.1 - FAR 52.246-9 - INSPECTION OF RESEARCH AND DEVELOPMENT (SHORT FORM) (APR 1984) The Government has the right to inspect and evaluate the work performed or being performed under

Supramolecular self-assembly on well-defined surfaces provides access to a multitude of nanoscale architectures, including clusters of distinct symmetry and size. The driving forces underlying supramolecular structures generally involve both graphoepitaxy and weak directional nonconvalent interactions. Here we show that functionalizing a benzene molecule with an ethyne group introduces attractive interactions in a 2D geometry, which would otherwise be dominated by intermolecular repulsion. Furthermore, the attractive interactions enable supramolecular self-assembly, wherein a subtle balance between very weak CH/{pi} bonding and molecule-surface interactions produces a well-defined 'magic' dimension and chirality of supramolecular clusters. The nature of the process is corroborated by extensive scanning tunneling microscopy/spectroscopy (STM/S) measurements and ab initio calculations, which emphasize the cooperative, multicenter characters of the CH/{pi} interaction. This work points out new possibilities for chemical functionalization of {pi}-conjugated hydrocarbon molecules that may allow for the rational design of supramolecular clusters with a desired shape and size.

Carbon flux data are reported as Net Ecosystem Exchange (NEE), Gross Ecosystem Exchange (GEE), Ecosystem Respiration (ER), and Methane (CH4) flux. Measurements were made at 82 plots across various polygon geomorphic classes at research sites on the Barrow Environmental Observatory (BEO), the Biocomplexity Experiment site on the BEO, and the International Biological Program (IBP) site a little west of the BEO. This product is a compilation of data from 27 plots as presented in Lara et al. (2012), data from six plots presented in Olivas et al. (2010); and from 49 plots described in (Lara et al. 2014). Measurements were made during the peak of the growing seasons during 2006 to 2010. At each of the measurement plots (except Olivas et al., 2010) four different thicknesses of shade cloth were used to generate CO2 light response curves. Light response curves were used to normalize photosynthetically active radiation that is diurnally variable to a peak growing season average ~400 umolm-2sec-1. At the Olivas et al. (2010) plots, diurnal patterns were characterized by repeated sampling. CO2 measurements were made using a closed-chamber photosynthesis system and CH4 measurements were made using a photo-acoustic multi-gas analyzer. In addition, plot-level measurements for thaw depth (TD), water table depth (WTD), leaf area index (LAI), and normalized difference vegetation index (NDVI) are summarized by geomorphic polygon type.

We present results from calculations of the physical conditions necessary for the occurrence of 36.169 (4{sub Ė1}-3{sub 0} E), 44.070 (7{sub 0}-6{sub 1} A {sup +}), 84.521 (5{sub Ė1}-4{sub 0} E), and 95.169 (8{sub 0}-7{sub 1} A {sup +}) GHz methanol (CH{sub 3}OH) maser emission lines near supernova remnants (SNRs), using the MOLPOP-CEP program. The calculations show that given a sufficient methanol abundance, methanol maser emission arises over a wide range of densities and temperatures, with optimal conditions at n ? 10{sup 4}-10{sup 6} cm{sup Ė3} and T > 60 K. The 36 GHz and 44 GHz transitions display more significant maser optical depths compared to the 84 GHz and 95 GHz transitions over the majority of physical conditions. It is also shown that line ratios are an important and applicable probe of the gas conditions. The line ratio changes are largely a result of the E-type transitions becoming quenched faster at increasing densities. The modeling results are discussed using recent observations of CH{sub 3}OH and hydroxyl (OH) masers near the SNRs G1.4Ė0.1, W28, and Sgr A East.

Carbon flux data are reported as Net Ecosystem Exchange (NEE), Gross Ecosystem Exchange (GEE), Ecosystem Respiration (ER), and Methane (CH4) flux. Measurements were made at 82 plots across various polygon geomorphic classes at research sites on the Barrow Environmental Observatory (BEO), the Biocomplexity Experiment site on the BEO, and the International Biological Program (IBP) site a little west of the BEO. This product is a compilation of data from 27 plots as presented in Lara et al. (2012), data from six plots presented in Olivas et al. (2010); and from 49 plots described in (Lara et al. 2014). Measurements were made during the peak of the growing seasons during 2006 to 2010. At each of the measurement plots (except Olivas et al., 2010) four different thicknesses of shade cloth were used to generate CO2 light response curves. Light response curves were used to normalize photosynthetically active radiation that is diurnally variable to a peak growing season average ~400 umolm-2sec-1. At the Olivas et al. (2010) plots, diurnal patterns were characterized by repeated sampling. CO2 measurements were made using a closed-chamber photosynthesis system and CH4 measurements were made using a photo-acoustic multi-gas analyzer. In addition, plot-level measurements for thaw depth (TD), water table depth (WTD), leaf area index (LAI), and normalized difference vegetation index (NDVI) are summarized by geomorphic polygon type.

In August-October 2012 and June-October 2013, co-located measurements were made of surface CH4 and CO2 flux, soil pore space concentrations and stable isotope compositions of CH4 and CO2, and subsurface temperature and soil moisture. Measurements were made in intensive study site 1 areas A, B, and C, and from the site 0 and AB transects, from high-centered, flat-centered, and low-centered polygons, from the center, edge, and trough of each polygon.

Activation by Cytochrome P450 | Stanford Synchrotron Radiation Lightsource Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond Activation by Cytochrome P450 Saturday, May 31, 2014 Cytochrome P450s (P450s) are a family of monooxygenase enzymes that are nearly ubiquitous in nature. P450s are often described as biological blowtorches due to their incredible oxidizing power:1 They can hydroxylate C-H bonds of about 98-100 kcal/mol. P450s are responsible for the phase I metabolism

Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has

We report on the discovery of the methoxy radical (CH{sub 3}O) toward the cold and dense core B1-b based on the observation, with the IRAM 30 m radio telescope, of several lines at 3 and 2 mm wavelengths. Besides this new molecular species we also report on the detection of many lines arising from methyl mercaptan (CH{sub 3}SH), formic acid (HCOOH), propynal (HCCCHO), acetaldehyde (CH{sub 3}CHO), dimethyl ether (CH{sub 3}OCH{sub 3}), methyl formate (CH{sub 3}OCOH), and the formyl radical (HCO). The column density of all these species is {approx_equal}10{sup 12} cm{sup -2}, corresponding to abundances of {approx_equal}10{sup -11}. The similarity in abundances for all these species strongly suggest that they are formed on the surface of dust grains and ejected to the gas phase through non-thermal desorption processes, most likely cosmic rays or secondary photons. Nevertheless, laboratory experiments indicate that the CH{sub 3}O isomer released to the gas phase is CH{sub 2}OH rather than the methoxy one. Possible gas-phase formation routes to CH{sub 3}O from OH and methanol are discussed.

Department of Energy award number DE-FC07-99CH11010, Enhanced Utilization of Corn Based Biomaterials, supported a technology development program sponsored by Cargill Dow LLC from September 30, 1999 through June 30, 2003. The work involved fundamental scientific studies on poly lactic acid (PLA), a new environmentally benign plastic material from renewable resources. DOE funds supported academic research at the Colorado School of Mines and the National Renewable Energy Laboratory (NREL), and industry cost share was directed towards applied research into new product development utilizing the fundamental information generated by the academic partners. Under the arrangement of the grant, the fundamental information is published so that other companies can utilize it in evaluating the applicability of PLA in their own products. The overall project objective is to increase the utilization of PLA, a renewable resource based plastic, currently produced from fermented corn sugar.

The genomic location and function of most distant-acting transcriptional enhancers in the human genome remains unknown We performed ChIP-seq for various transcriptional coactivator proteins (such as p300) directly from different embryonic mouse tissues, identifying thousands of binding sitesTransgenic mouse experiments show that p300 and other co-activator peaks are highly predictive of genomic location AND tissue-specific activity patterns of distant-acting enhancersMost enhancers are active only in one or very few tissues Genomic location of tissue-specific p300 peaks correlates with tissue-specific expression of nearby genes Most binding sites are conserved, but the global degree of conservation varies between tissues

We have used the Karl G. Jansky Very Large Array to search for 36 GHz and 44 GHz methanol (CH{sub 3}OH) lines in a sample of 21 Galactic supernova remnants (SNRs). Mainly the regions of the SNRs with 1720 MHz OH masers were observed. Despite the limited spatial extent covered in our search, methanol masers were detected in both G1.4Ė0.1 and W28. Additional masers were found in Sgr A East. More than 40 masers were found in G1.4Ė0.1, which we deduce are due to interactions between the SNR and at least two separate molecular clouds. The six masers in W28 are associated with the molecular cloud that is also associated with the OH maser excitation. We discuss the possibility that the methanol maser may be more numerous in SNRs than the OH maser, but harder to detect due to observational constraints.

In this work we make an investigation on collision dynamics of H{sup +} + CH{sub 4} at 30 eV by using time-dependent density functional theory coupled with molecular dynamics approach. All possible reactions are presented based on 9 incident orientations. The calculated fragment intensity is in nice agreement with experimental results. The mechanism of reaction transition for dissociation and proton exchange processes is explained by the intra-molecule energy transfer. However, the energy loss of the proton is in poor agreement with experimental results. The discrepancy is attributed to the mean-field treatment of potential surface. We also studied the dependence on initial velocity of both proton and methane. In addition, we find that for dynamical evolution a different self-interaction correction (SIC) may lead to different results, but with respect to the position of rainbow angle, average-density SIC seems to have reasonable correction.

A diode laser spectrometer incorporating a multi-pass Herriott type cell and frequency modulation detection was used to record a previously unaccessed region of the near-infrared singlet{l_arrow}singlet absorption spectrum of methylene between 10thinsp000 cm{sup {minus}1} and 10thinsp600 cm{sup {minus}1}. With this spectrometer, signal-to-noise ratios close to the quantum noise limit have been attained. Identification of rovibronic transitions to five previously unobserved levels, K=1 {tilde a}(0,9,0), K=2thinsp{tilde b}(0,1,0), K=2thinsp{tilde a}(1,6,0), K=3thinsp{tilde b}(0,1,0) and K=3thinsp{tilde a}(0,10,0), was made. Despite the fact that the present spectra access levels within approximately 1300 cm{sup {minus}1} of the barrier to linearity, the spectrum is dense and perturbed, characteristics in common with spectra recorded in many previous studies at shorter wavelengths. Recent spectroscopic observations of halomethylenes [J. Mol. Spectrosc. {bold 188}, 68 (1998)] had suggested that the CH{sub 2} spectrum might become simpler at longer wavelengths, but this was not evident in the observed spectra. The mixed nature of the singlet states is evidenced by the assignment of rovibronic transitions to levels containing primarily {tilde a}thinsp{sup 1}A{sub 1} state character. The new measurements provide a stringent test for modern theoretical models for CH{sub 2} and will enable refinement of the electronic potential surfaces. {copyright} {ital 1998 American Institute of Physics.}

An alkyl-substituted Criegee intermediate syn-CH{sub 3}CHOO was detected in the gas phase through Fourier-transform microwave spectroscopy. Observed pure rotational transitions show a small splitting corresponding to the A/E components due to the threefold methyl internal rotation. The rotational constants and the barrier height of the hindered methyl rotation were determined to be A = 17?586.5295(15) MHz, B = 7133.4799(41) MHz, C = 5229.1704(40) MHz, and V{sub 3} = 837.1(17)†cm{sup ?1}. High-level ab initio calculations which reproduce the experimentally determined values well indicate that the in-plane CĖH bond in the methyl moiety is trans to the CĖO bond, and other two protons are directed to the terminal oxygen atom for the most stable structure of syn-CH{sub 3}CHOO. The torsional barrier of the methyl top is fairly large in syn-CH{sub 3}CHOO, implying a significant interaction between the terminal oxygen and the protons of the methyl moiety, which may be responsible for the high production yields of the OH radical from energized alkyl-substituted Criegee intermediates.

The reaction between Cl atoms and CH{sub 3}OCl was investigated at 295 K in both air and N{sub 2} bath gases at total pressures between 100 and 850 Torr by the relative rate method. The rate constant of the title reaction was found to be a factor 1.07{+-}0.02 (2{sigma}) greater than that of Cl+C{sub 2}H{sub 6} at room temperature and independent of pressure between 100 and 750 Torr. This yields a rate constant of (6.1{+-}0.6)x10{sup -11} cm{sup 3} molecule{sup -1} s{sup -1}. The products of the reaction were detected by FTIR and UV absorption spectroscopy. Analysis of Cl{sub 2} and HCl products allowed branching ratios of 0.2{+-}0.1 for HCl+CH{sub 2}OCl formation and 0.8{+-}0.2 for Cl{sub 2}+CH{sub 3}O formation to be determined. The high rate constant implies that reaction with Cl atoms is an important loss process for CH{sub 3}OCl in the polar stratosphere. 37 refs., 9 figs., 3 tabs.

We report a rigorous variational study of the infrared (IR) vibrational spectra of both CH{sub 2}D{sub 2} and {sup 13}CH{sub 2}D{sub 2} isotopomers using an exact molecular Hamiltonian. Calculations are carried out using a recently developed multi-layer Lanczos algorithm based on the accurate refined Wang and Carrington potential energy surface of methane and the low-order truncated ab initio dipole moment surface of Yurchenko et al. [J. Mol. Spectrosc. 291, 69 (2013)]. All well converged 357 vibrational energy levels up to 6100 cm{sup ?1} of CH{sub 2}D{sub 2} are obtained, together with a comparison to previous calculations and 91 experimental bands available. The calculated frequencies are in excellent agreement with the experimental results and give a root-mean-square error of 0.67?cm{sup ?1}. In particular, we also compute the transition intensities from the vibrational ground state for both isotopomers. Based on the theoretical results, 20 experimental bands are suggested to be re-assigned. Surprisingly, an anomalous C isotopic effect is discovered in the n?{sub 5} modes of CH{sub 2}D{sub 2}. The predicted IR spectra provide useful information for understanding those unknown bands.

DOE's Oak Ridge Environmental Management Office told URS | CH2M Oak Ridge LLC (UCOR) in a letter that it had completed its evaluation of the company's performance for the award fee period of April to September 2015 and determined that UCOR earned a fee of more than $4.4 million for the period.

The effects of CO addition on the characteristics of premixed CH{sub 4}/air opposed-jet flames are investigated experimentally and numerically. Experimental measurements and numerical simulations of the flame front position, temperature, and velocity are performed in stoichiometric CH{sub 4}/CO/air opposed-jet flames with various CO contents in the fuel. Thermocouple is used for the determination of flame temperature, velocity measurement is made using particle image velocimetry (PIV), and the flame front position is measured by direct photograph as well as with laser-induced predissociative fluorescence (LIPF) of OH imaging techniques. The laminar burning velocity is calculated using the PREMIX code of Chemkin collection 3.5. The flame structures of the premixed stoichiometric CH{sub 4}/CO/air opposed-jet flames are simulated using the OPPDIF package with GRI-Mech 3.0 chemical kinetic mechanisms and detailed transport properties. The measured flame front position, temperature, and velocity of the stoichiometric CH{sub 4}/CO/air flames are closely predicted by the numerical calculations. Detailed analysis of the calculated chemical kinetic structures reveals that as the CO content in the fuel is increased from 0% to 80%, CO oxidation (R99) increases significantly and contributes to a significant level of heat-release rate. It is also shown that the laminar burning velocity reaches a maximum value (57.5 cm/s) at the condition of 80% of CO in the fuel. Based on the results of sensitivity analysis, the chemistry of CO consumption shifts to the dry oxidation kinetics when CO content is further increased over 80%. Comparison between the results of computed laminar burning velocity, flame temperature, CO consumption rate, and sensitivity analysis reveals that the effect of CO addition on the laminar burning velocity of the stoichiometric CH{sub 4}/CO/air flames is due mostly to the transition of the dominant chemical kinetic steps. (author)

Abstract The sequestration of carbon dioxide (CO2) in deep underground reservoirs has been identified as an important strategy to decrease atmospheric CO2 levels and mitigate global warming, but potential risks on overlying aquifers currently lack a complete evaluation. In addition to CO2, other gases such as methane (CH4) may be present in storage reservoirs. This paper explores for the first time the combined effect of leaking CO2 and CH4 gasses on the fate of major, minor and trace elements in an aquifer overlying a potential sequestration site. Emphasis is placed on the fate of arsenic (As) and cadmium (Cd) released from the sediments or present as soluble constituents in the leaking brine. Results from macroscopic batch and column experiments show that the presence of CH4 (at a concentration of 1 % in the mixture CO2/CH4) does not have a significant effect on solution pH or the concentrations of most major elements (such as Ca, Ba, and Mg). However, the concentrations of Mn, Mo, Si and Na are inconsistently affected by the presence of CH4 (i.e., in at least one sediment tested in this study). Cd is not released from the sediments and spiked Cd is mostly removed from the aqueous phase most likely via adsorption. The fate of sediment associated As [mainly sorbed arsenite or As(III) in minerals] and spiked As [i.e., As5+] is complex. Possible mechanisms that control the As behavior in this system are discussed in this paper. Results are significant for CO2 sequestration risk evaluation and site selection and demonstrate the importance of evaluating reservoir brine and gas stream composition during site selection to ensure the safest site is being chosen.

Despite great theoretical and technological interest in polyacetylene, (CH){sub x}, the basic features of its band structure have not been unambiguously resolved. Since photoconductivity and optical absorption data have frequently been used to infer information on the band structure of semiconductors, such measurements were carried out on (CH){sub x}. The main results of an extensive study of the photoconductivity (..delta.. sigma{sub ph}) and absorption coefficient (..cap alpha..) in (CH){sub x} are presented. The absence of photoconductivity in cis-(CH){sub x}, despite the similarity in optical properties indicates that ..delta.. sigma/sub ph/ in trans-(CH){sub x} is induced by isomerization. It is found that isomerization generates states deep inside the gap that act as safe traps for minority carriers and thereby enhance the photoconductivity. Compensation of trans-(CH){sub x} with ammonia appears to decrease the number of safe traps, whereas acceptor doping increases their number. Thus, chemical doping can be used to control the photoconductive response. The energy of safe traps inside the gap is independent of the process used to generate them; indicative of an intrinsic localized defect level in trans-(CH){sub x}. A coherent picture based on the soliton model can explain these results, including the safe trapping.

Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

An eight-dimensional quantum dynamical model is proposed and applied to the title reaction. The reaction probabilities and integral cross sections have been determined for both the ground and excited vibrational states of the two reactants. The results indicate that the H{sub 2} stretching and CH{sub 3} umbrella modes, along with the translational energy, strongly promote the reactivity, while the CH{sub 3} symmetric stretching mode has a negligible effect. The observed mode specificity is confirmed by full-dimensional quasi-classical trajectory calculations. The mode specificity can be interpreted by the recently proposed sudden vector projection model, which attributes the enhancement effects of the reactant modes to their strong couplings with the reaction coordinate at the transition state.

A pyrrolyl-based triazolophane, incorporating CH and NH donor groups, acts as a receptor for the pyrophosphate anion in chloroform solution. It shows selectivity for this trianion, followed by HSO{sub 4}{sup -} > H{sub 2}PO{sub 4}{sup -} > Cl{sup -} > Br{sup -} (all as the corresponding tetrabutylammonium salts), with NH-anion interactions being more important than CH-anion interactions. In the solid state, the receptor binds the pyrophosphate anion in a clip-like slot via NH and CH hydrogen bonds.

It has been proposed that ZNF217, which is amplified at 20q13 in various tumors, plays a key role during neoplastic transformation. ZNF217 has been purified in complexes that contain repressor proteins such as CtBP2, suggesting that it acts as a transcriptional repressor. However, the function of ZNF217 has not been well characterized due to a lack of known target genes. Using a global chromatin immunoprecipitation (ChIP)-chip approach, we identified thousands of ZNF217 binding sites in three tumor cell lines (MCF7, SW480, and Ntera2). Further analysis of ZNF217 in Ntera2 cells showed that many promoters are bound by ZNF217 and CtBP2 and that a subset of these promoters are activated upon removal of ZNF217. Thus, our in vivo studies corroborate the in vitro biochemical analyses of ZNF217-containing complexes and support the hypothesis that ZNF217 functions as a transcriptional repressor. Gene ontology analysis showed that ZNF217 targets in Ntera2 cells are involved in organ development, suggesting that one function of ZNF217 may be to repress differentiation. Accordingly we show that differentiation of Ntera2 cells with retinoic acid led to down-regulation of ZNF217. Our identification of thousands of ZNF217 target genes will enable further studies of the consequences of aberrant expression of ZNF217 during neoplastic transformation.

The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

Here, formaldehyde measurements from two independent instruments are compared with photochemical box model calculations. The measurements were made on the NOAA P-3 aircraft as part of the 1997 North Atlantic Regional Experiment (NARE 1997). After examining the possible reasons for the model-measurement discrepancy, we conclude that there are probably one or more additional unknown sources of CH2O in the North Atlantic troposphere.

The single crystal X-ray diffraction structure of [(CH3)4N]2PuCl6 is presented for the first time, resolving long standing confusion and speculation regarding the structure of this compound in the literature. A temperature dependent study of this compound shows that the structure of [(CH3)4N]2PuCl6 undergoes no fewer than two phase transitions between 100 and 360 K. The phase of [(CH3)4N]2PuCl6 at room temperature is Fd-3c a = 26.012(3) √Ö. At 360 K, the structure is in space group Fm-3m with a = 13.088(1) √Ö. The plutonium octahedra and tetramethylammonium cations undergo a rotative displacement and the degree of rotation varies with temperature, giving rise to the phase transition from Fm-3m to Fd-3c as the crystal is cooled. Synthesis and structural studies of the deuterated salt [(CD3)4N]2PuCl6 suggest that there is an isotopic effect associated with this phase transition as revealed by a changing transition temperature in the deuterated versus protonated compound indicating that the donor-acceptor interactions between the tetramethylammonium cations and the hexachloroplutonate anions are driving the phase transformation.

Soil microbial metabolic activities play an important role in determining CO{sub 2}, CH{sub 4}, and N{sub 2}O fluxes from terrestrial ecosystems. To verify and evaluate CO{sub 2} sequestration potential by wetland restoration in the Prairie Pothole Region (PPR), as well as to address concern over restoration effects on CH{sub 4} and N{sub 2}O emissions, laboratory and in situ microcosm studies on microbial cycling of CO{sub 2}, CH{sub 4}, and N{sub 2}O were initiated. In addition, to evaluate the feasibility of the use of remote sensing to detect soil gas flux from wetlands, a remote-sensing investigation was also conducted. Results of the laboratory microcosm study unequivocally proved that restoration of PPR wetlands does sequester atmospheric CO{sub 2}. Under the experimental conditions, the simulated restored wetlands did not promote neither N{sub 2}O nor CH{sub 4} fluxes. Application of ammonia enhanced both N{sub 2}O and CH{sub 4} emission, indicating that restoration of PPR wetlands may reduce both N{sub 2}O and CH{sub 4} emission by cutting N-fertilizer input. Enhancement of CO{sub 2} emission by the N-fertilizer was observed, and this observation revealed an overlooked fact that application of N-fertilizer may potentially increase CO{sub 2} emission. In addition, the CO{sub 2} results also demonstrate that wetland restoration sequesters atmospheric carbon not only by turning soil conditions from aerobic to anoxic, but also by cutting N-fertilizer input that may enhance CO{sub 2} flux. The investigation on microbial community structure and population dynamics showed that under the experimental conditions restoration of the PPR wetlands would not dramatically increase population sizes of those microorganisms that produce N{sub 2}O and CH{sub 4}. Results of the in situ study proved that restoration of the PPR wetland significantly reduced CO{sub 2} flux. Ammonia enhanced the greenhouse gas emission and linearly correlated to the CO{sub 2} flux within the

Vibrational infrared (IR) spectra of gas-phase OĖH???O methanol clusters up to pentamer are simulated using self-consistent-charge density functional tight-binding method using two distinct methodologies: standard normal mode analysis and Fourier transform of the dipole time-correlation function. The twofold simulations aim at the direct critical assignment of the CĖH stretching region of the recently recorded experimental spectra [H.-L. Han, C. Camacho, H. A. Witek, and Y.-P. Lee, J. Chem. Phys. 134, 144309 (2011)]. Both approaches confirm the previous assignment (ibid.) of the CĖH stretching bands based on the B3LYP/ANO1 harmonic frequencies, showing that ?{sub 3}, ?{sub 9}, and ?{sub 2} CĖH stretching modes of the proton-accepting (PA) and proton-donating (PD) methanol monomers experience only small splittings upon the cluster formation. This finding is in sharp discord with the assignment based on anharmonic B3LYP/VPT2/ANO1 vibrational frequencies (ibid.), suggesting that some procedural faults, likely related to the breakdown of the perturbational vibrational treatment, led the anharmonic calculations astray. The IR spectra based on the Fourier transform of the dipole time-correlation function include new, previously unaccounted for physical factors such as non-zero temperature of the system and large amplitude motions of the clusters. The elevation of temperature results in a considerable non-homogeneous broadening of the observed IR signals, while the presence of large-amplitude motions (methyl group rotations and PA-PD flipping), somewhat surprisingly, does not introduce any new features in the spectrum.

The objective of this short-term LDRD project was to acquire the tools needed to use our chemical imaging precision mass analyzer (ChIPMA) instrument to analyze tissue samples. This effort was an outgrowth of discussions with oncologists on the need to find the cellular origin of signals in mass spectra of serum samples, which provide biomarkers for ovarian cancer. The ultimate goal would be to collect chemical images of biopsy samples allowing the chemical images of diseased and nondiseased sections of a sample to be compared. The equipment needed to prepare tissue samples have been acquired and built. This equipment includes an cyro-ultramicrotome for preparing thin sections of samples and a coating unit. The coating unit uses an electrospray system to deposit small droplets of a UV-photo absorbing compound on the surface of the tissue samples. Both units are operational. The tissue sample must be coated with the organic compound to enable matrix assisted laser desorption/ionization (MALDI) and matrix enhanced secondary ion mass spectrometry (ME-SIMS) measurements with the ChIPMA instrument Initial plans to test the sample preparation using human tissue samples required development of administrative procedures beyond the scope of this LDRD. Hence, it was decided to make two types of measurements: (1) Testing the spatial resolution of ME-SIMS by preparing a substrate coated with a mixture of an organic matrix and a bio standard and etching a defined pattern in the coating using a liquid metal ion beam, and (2) preparing and imaging C. elegans worms. Difficulties arose in sectioning the C. elegans for analysis and funds and time to overcome these difficulties were not available in this project. The facilities are now available for preparing biological samples for analysis with the ChIPMA instrument. Some further investment of time and resources in sample preparation should make this a useful tool for chemical imaging applications.

Optimized geometries, S-OO bond dissociation energies and enthalpies of formation for a series of thiomethyl peroxyl radicals are investigated using high level ab initio and density functional theory methods. The results show that the S-OO bond dissociation energy is largest in the methylsulfonyl peroxyl radical, CH{sub 3}S(O){sub 2}OO, which contains two sulfonic type oxygen atoms followed by the methylthiyl peroxyl radical, CH{sub 3}SOO. The methylsulfinyl peroxyl radical, CH{sub 3}S(O)OO, which contains only one sulfonic type oxygen shows the least stability with regard to dissociation to CH{sub 3}S(O)+O{sub 2}. This stabilization trend is nicely reflected in the variations of the S-OO bond distance which is found to be shortest in CH{sub 3}S(O){sub 2}OO and longest in CH{sub 3}S(O)OO.

Experiments are presented, which demonstrate the properties of x-ray radiation and redistribution of radiant thermal energy in high Z cylindrical cavities filled with low Z CH foam. Time integrated spectra records were obtained by a calibrated space-resolved transmission grating spectrometer. The x-ray radiation became weaker in intensity and was changed to a softer near-Planckian radiation light after a 1500 {mu}m long transport in the foam filling cavity. The experimental redistribution of the radiant thermal energy was plotted and compared to the numerical results of a simplified model. Good agreements have been achieved.

The Justice Department, in conjunction with the U.S. Attorney‚Äôs Office for the Eastern District of Washington, announced today that Colorado-based CH2M Hill Hanford Group Inc. (CHG) and its parent company, CH2M Hill Companies Ltd. (CH2M Hill) have agreed that CHG committed federal criminal violations, defrauding the public by engaging in years of widespread time card fraud.

We have recorded the complete infrared spectrum of methane {sup 12}CH{sub 4} and its second most abundant isotopomer {sup 13}CH{sub 4} extending from the fundamental range starting at 1000 cm{sup ?1} up to the overtone region near 12†000 cm{sup ?1} in the near infrared at the limit towards the visible range, at temperatures of about 80 K and also at 298 K with Doppler limited resolution in the gas phase by means of interferometric Fourier transform spectroscopy using the Bruker IFS 125 HR prototype (ZP 2001) of the ETH ZŁrich laboratory. This provides the so far most complete data set on methane spectra in this range at high resolution. In the present work we report in particular those results, where the partial rovibrational analysis allows for the direct assignment of pure (J = 0) vibrational levels including high excitation. These results substantially extend the accurate knowledge of vibrational band centers to higher energies and provide a benchmark for both the comparison with theoretical results on the one hand and atmospheric spectroscopy on the other hand. We also present a simple effective Hamiltonian analysis, which is discussed in terms of vibrational level assignments and {sup 13}C isotope effects.

Initial state-selected reaction probabilities of the H + CH{sub 4} ? H{sub 2} + CH{sub 3} reaction are calculated in full and reduced dimensionality on a recent neural network potential [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. The quantum dynamics calculation employs the quantum transition state concept and the multi-layer multi-configurational time-dependent Hartree approach and rigorously studies the reaction for vanishing total angular momentum (J = 0). The calculations investigate the accuracy of the neutral network potential and study the effect resulting from a reduced-dimensional treatment. Very good agreement is found between the present results obtained on the neural network potential and previous results obtained on a Shepard interpolated potential energy surface. The reduced-dimensional calculations only consider motion in eight degrees of freedom and retain the C{sub 3v} symmetry of the methyl fragment. Considering reaction starting from the vibrational ground state of methane, the reaction probabilities calculated in reduced dimensionality are moderately shifted in energy compared to the full-dimensional ones but otherwise agree rather well. Similar agreement is also found if reaction probabilities averaged over similar types of vibrational excitation of the methane reactant are considered. In contrast, significant differences between reduced and full-dimensional results are found for reaction probabilities starting specifically from symmetric stretching, asymmetric (f{sub 2}-symmetric) stretching, or e-symmetric bending excited states of methane.

Effects of one-quantum excitation of the antisymmetric-stretching mode of CH{sub 4}(v{sub 3} = 1) on the O({sup 3}P) + CH{sub 4} reaction were studied in a crossed-beam, ion-imaging experiment. In the post-threshold region, we found that (1) the product state distributions are dominated by the CH{sub 3}(0{sub 0}) + OH(v{sup ?} = 1) pair, (2) the product angular distributions extend toward sideways from the backward dominance of the ground-state reaction, and (3) vibrational excitation exerts a positive effect on reactivity, but translational energy is more efficient in promoting the rate of this central-barrier reaction. All major findings agree reasonably well with recent theoretical results. Some remaining questions are pointed out.

The fragmentation dynamics of CH{sub 4} and H{sub 2}CO molecules have been studied with ultra-short pulses at laser intensityof up to 10{sup 15}Wcm{sup ‚ąí2}. Three dimensional molecular dynamics calculations for finding the optimized laser pulses are presented based on time-dependent density functional theory and quantum optimal control theory. A comparison of the results for orientation dependence in the ionization process shows that the electron distribution for CH{sub 4} is more isotropic than H{sub 2}CO molecule. Total conversion yields of up to 70% at an orientation angle of 30{sup o} for CH{sub 4} and 65% at 90{sup 0} for H{sub 2}CO are achieved which lead to enhancement of dissociation probability.

Pure rotational transitions of hydroxymethyl hydroperoxide (HMHP) were observed in the discharged plasma of a CH{sub 2}I{sub 2}/O{sub 2}/water gas mixture, where the water complex with the simplest Criegee intermediate CH{sub 2}OO has been identified [M. Nakajima and Y. Endo, J. Chem. Phys. 140, 134302 (2014)]. Isotope experiments using heavy water support that the currently observed HMHP molecule was produced by the reaction of CH{sub 2}OO with water vapor. The observed species was identified as the most stable conformer with the help of quantum chemical calculations. We also clarified that productions of formic acid and dioxirane are promoted by the existence of water vapor in the discharged reaction system.

The vibrationally excited reaction of F + CHD{sub 3}(őĹ{sub 1} = 1) ‚Üí DF + CHD{sub 2} at a collision energy of 9.0 kcal/mol is investigated using the crossed-beams and time-sliced velocity map imaging techniques. Detailed and quantitative information of the CH stretching excitation effects on the reactivity and dynamics of the title reaction is extracted with the help of an accurate determination of the fraction of the excited CHD{sub 3} reagent in the crossed-beam region. It is found that all vibrational states of the CHD{sub 2} products observed in the ground-state reaction, which mainly involve the excitation of the umbrella mode of the CHD{sub 2} products, are severely suppressed by the CH stretching excitation. However, there are four additional vibrational states of the CHD{sub 2} products appearing in the excited-state reaction which are not presented in the ground-state reaction. These vibrational states either have the CH stretching excitation retained or involve one quantum excitation in the CH stretching and the excitation of the umbrella mode. Including all observed vibrational states, the overall cross section of the excited-state reaction is estimated to be 66.6% of that of the ground-state one. Experimental results also show that when the energy of CH stretching excitation is released during the reaction, it is deposited almost exclusively as the rovibrational energy of the DF products, with little portion in the translational degree of freedom. For vibrational states of the CHD{sub 2} products observed in both ground- and excited-state reactions, the CH stretching excitation greatly suppresses the forward scattered products, causing a noticeable change in the product angular distributions.

The space weathering of icy Kuiper Belt Objects was investigated in this case study by exposing methane (CH{sub 4}) and carbon monoxide (CO) doped nitrogen (N{sub 2}) ices at 10 K to ionizing radiation in the form of energetic electrons. Online and in situ Fourier transform infrared spectroscopy was utilized to monitor the radiation-induced chemical processing of these ices. Along with isocyanic acid (HNCO), the products could be mainly derived from those formed in irradiated binary ices of the N{sub 2}-CH{sub 4} and CO-CH{sub 4} systems: nitrogen-bearing products were found in the form of hydrogen cyanide (HCN), hydrogen isocyanide (HNC), diazomethane (CH{sub 2}N{sub 2}), and its radical fragment (HCN{sub 2}); oxygen-bearing products were of acetaldehyde (CH{sub 3}CHO), formyl radical (HCO), and formaldehyde (H{sub 2}CO). As in the pure ices, the methyl radical (CH{sub 3}) and ethane (C{sub 2}H{sub 6}) were also detected, as were carbon dioxide (CO{sub 2}) and the azide radical (N{sub 3}). Based on the temporal evolution of the newly formed products, kinetic reaction schemes were then developed to fit the temporal profiles of the newly formed species, resulting in numerical sets of rate constants. The current study highlights important constraints on the preferential formation of isocyanic acid (HNCO) over hydrogen cyanide (HCN) and hydrogen isocyanide (HNC), thus guiding the astrobiological and chemical evolution of those distant bodies.

Silver-exchanged mordenite (AgZ) has been identified as a potential sorbent for iodine present in the off-gas streams of a used nuclear fuel reprocessing facility. In such a facility, both elemental and organic forms of iodine are released from the dissolver in gaseous form. These species of iodine must be captured with high efficiency for a facility to avoid radioactive iodine release above regulatory limits in the gaseous effluent of the plant. Studies completed at Idaho National Laboratory (INL) examined the adsorption of organic iodine in the form of CH3I by AgZ. Upon breakthrough of the feed gas through the sorbent bed, elemental iodine was observed in the effluent stream, despite the fact that the only source of iodine in the system was the CH3I in the feed gas.1 This behavior does not appear to have been reported previously nor has it been independently confirmed. Thus, as a result of these prior studies, multiple knowledge gaps relating to the adsorption of CH3I by AgZ were identified, and a multi-lab test plan, including Oak Ridge National Laboratory (ORNL), INL, Pacific Northwest National Laboratory (PNNL), and Sandia National Laboratories, was formulated to address each in a systematic way.2 For this report, the scope of work for ORNL was further narrowed to three thin-bed experiments that would characterize CH3I adsorption onto AgZ in the presence of water, NO, and NO2. Completion of these three-thin bed experiments demonstrated that organic iodine in the form of CH3I was adsorbed by reduced silver mordenite (Ag0Z) to a 50% higher loading than that of I2 when adsorbed from a dry air stream. Adsorption curves suggest different adsorption mechanisms for I2 and CH3I. In the presence of NO and NO2 gas, the loading of CH3I onto Ag0Z is suppressed and may be reversible. Further, the presence of NO and NO2 gas appears to oxidize CH3I to I2; this is indicated by an adsorption curve similar to that of I2 on Ag0Z. Finally, the loss of organic iodine loading

Halide-perovskite CH{sub 3}NH{sub 3}PbI{sub 3} was produced on mesoporous TiO{sub 2} layer by spin-coating a precursor solution of PbCl{sub 2} and CH{sub 3}NH{sub 3}I in dimethylformamide. The role of the annealing process and chlorine (Cl) doping for the perovskite-phase formation was investigated. It was found that crystallization of the perovskite materials was stimulated by the annealing process, and that longer annealing time is necessary for the Cl-doped perovskite compared with that of non-doped perovskite phase.

The Ignik Sikumi Gas Hydrate Exchange Field Trial was conducted by ConocoPhillips in partnership with the U.S. Department of Energy, the Japan Oil, Gas, and Metals National Corporation, and the U.S. Geological Survey within the Prudhoe Bay Unit on the Alaska North Slope (ANS) during 2011 and 2012. The 2011 field program included drilling the vertical test well and performing extensive wireline logging through a thick section of gas-hydrate-bearing sand reservoirs that provided substantial new insight into the nature of ANS gas hydrate occurrences. The 2012 field program involved an extended, scientific field trial conducted within a single vertical well (‚Äúhuff-and-puff‚ÄĚ design) through three primary operational phases: 1) injection of a gaseous phase mixture of CO2, N2, and chemical tracers; 2) flowback conducted at down-hole pressures above the stability threshold for native CH4-hydrate, and 3) extended (30-days) flowback at pressures below the stability threshold of native CH4-hydrate. Ignik Sikumi represents the first field investigation of gas hydrate response to chemical injection, and the longest-duration field reservoir response experiment yet conducted. Full descriptions of the operations and data collected have been fully reported by ConocoPhillips and are available to the science community. The 2011 field program indicated the presence of free water within the gas hydrate reservoir, a finding with significant implications to the design of the exchange trial ‚Äď most notably the use of a mixed gas injectant. While this decision resulted in a complex chemical environment within the reservoir that greatly tests current experimental and modeling capabilities ‚Äď without such a mixture, it is apparent that injection could not have been achieved. While interpretation of the field data are continuing, the primary scientific findings and implications of the program are: 1) gas hydrate destabilizing is self-limiting, dispelling any notion of the potential for

Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH3NH3PbBr3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4¬Ī0.1 103 cm s-1, B2‚Äď3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggests that the planar grain sizemore¬†¬Ľ for the perovskite thin films should be larger thanB30 mm to avoid the influence of surface recombination on the effective carrier lifetime.¬ę¬†less

Combined with a Herriott-type multi-pass slow flow reactor, high-resolution differential direct absorption spectroscopy has been used to probe, in situ and quantitatively, hydroxyl (OH), hydroperoxy (HO 2 ) and formaldehyde (CH 2 O) molecules in fuel oxidation reactions in the reactor, with a time resolution of about 1 micro-second. While OH and CH 2 O are probed in the mid-infrared (MIR) region near 2870nm and 3574nm respectively, HO 2 can be probed in both regions: near-infrared (NIR) at 1509nm and MIR at 2870nm. Typical sensitivities are on the order of 10 10 - 10 11 molecule cm -3 for OH at 2870nm, 10 11 molecule cm -3 for HO 2 at 1509nm, and 10 11 molecule cm -3 for CH 2 O at 3574nm. Measurements of multiple important intermediates (OH and HO 2 ) and product (CH 2 O) facilitate to understand and further validate chemical mechanisms of fuel oxidation chemistry.

Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine their stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS{sub 2}). - Highlights: ‚ÄĘ Study of compositional stability of MTCh vs. M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} compounds. ‚ÄĘ Study of structural stability of known and novel MTCh compounds. ‚ÄĘ Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS{sub 2}.

By using time-resolved Fourier-transform infrared emission spectroscopy, the fragments of HCN(v= 1, 2) and CO(v= 1-3) are detected in one-photon dissociation of acetyl cyanide (CH{sub 3}COCN) at 308 nm. The S{sub 1}(A'), {sup 1}(n{sub O}, {pi}*{sub CO}) state at 308 nm has a radiative lifetime of 0.46 {+-} 0.01 {mu}s, long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of Ar collision-induced internal conversion is estimated to be (1-7) x 10{sup -12} cm{sup 3} molecule{sup -1} s{sup -1}. The measurements of O{sub 2} dependence exclude the production possibility of these fragments via intersystem crossing. The high-resolution spectra of HCN and CO are analyzed to determine the ro-vibrational energy deposition of 81 {+-} 7 and 32 {+-} 3 kJ/mol, respectively. With the aid of ab initio calculations, a two-body dissociation on the energetic ground state is favored leading to HCN + CH{sub 2}CO, in which the CH{sub 2}CO moiety may further undergo secondary dissociation to release CO. The production of CO{sub 2} in the reaction with O{sub 2} confirms existence of CH{sub 2} and a secondary reaction product of CO. The HNC fragment is identified but cannot be assigned, as restricted to a poor signal-to-noise ratio. Because of insufficient excitation energy at 308 nm, the CN and CH{sub 3} fragments that dominate the dissociation products at 193 nm are not detected.

One of the least understood properties of comets is the compositional structure of their nuclei, which can either be homogeneous or heterogeneous. The nucleus structure can be conveniently studied at millimeter wavelengths, using velocity-resolved spectral time series of the emission lines, obtained simultaneously for multiple molecules as the body rotates. Using this technique, we investigated the sources of CH{sub 3}OH and HCN in comet 103P/Hartley 2, the target of NASA's EPOXI mission, which had an exceptionally favorable apparition in late 2010. Our monitoring with the IRAM 30 m telescope shows short-term variability of the spectral lines caused by nucleus rotation. The varying production rates generate changes in brightness by a factor of four for HCN and by a factor of two for CH{sub 3}OH, and they are remarkably well correlated in time. With the addition of the velocity information from the line profiles, we identify the main sources of outgassing: two jets, oppositely directed in a radial sense, and icy grains, injected into the coma primarily through one of the jets. The mixing ratio of CH{sub 3}OH and HCN is dramatically different in the two jets, which evidently shows large-scale chemical heterogeneity of the nucleus. We propose a network of identities linking the two jets with morphological features reported elsewhere and postulate that the chemical heterogeneity may result from thermal evolution. The model-dependent average production rates are 3.5 Multiplication-Sign 10{sup 26} molecules s{sup -1} for CH{sub 3}OH and 1.25 Multiplication-Sign 10{sup 25} molecules s{sup -1} for HCN, and their ratio of 28 is rather high but not abnormal. The rotational temperature from CH{sub 3}OH varied strongly, presumably due to nucleus rotation, with the average value being 47 K.

InfraRed Tunable Diode Laser Absorption Spectroscopy technique has been implemented in a H{sub 2}/CH{sub 4} Micro-Wave (MW frequency f?=?2.45 GHz) plasma reactor dedicated to diamond deposition under high pressure and high power conditions. Parametric studies such as a function of MW power, pressure, and admixtures of methane have been carried out on a wide range of experimental conditions: the pressure up to 270 mbar and the MW power up to 4?kW. These conditions allow high purity Chemical Vapor Deposition diamond deposition at high growth rates. Line integrated absorption measurements have been performed in order to monitor hydrocarbon species, i.e., CH{sub 3}, CH{sub 4}, C{sub 2}H{sub 2}, C{sub 2}H{sub 4}, and C{sub 2}H{sub 6}. The densities of the stable detected species were found to vary in the range of 10{sup 12}Ė10{sup 17} molecules cm{sup ?3}, while the methyl radical CH{sub 3} (precursor of diamond growth under these conditions) measured into the plasma bulk was found up to 10{sup 14} molecules cm{sup ?3}. The experimental densities have been compared to those provided by 1D-radial thermochemical model for low power and low pressure conditions (up to 100 mbar/2?kW). These densities have been axially integrated. Experimental measurements under high pressure and power conditions confirm a strong increase of the degree of dissociation of the precursor, CH{sub 4}, associated to an increase of the C{sub 2}H{sub 2} density, the most abundant reaction product in the plasma.

An x-ray structural investigation of the structure of MoO2 (C6H5CONHO)2 x 2/3 CH3CH2COOH (I) has been carried out (diffractometer, Cu K/sub /, least-squares method in the anisotropic approximation to R = 0.053). The crystallographic data are: a = 17.290(2), c = 11.140(2) A, rho(exp) = 1.53, rho(calc) = 1.562(1) g/cmT, space group P61, Z = 6. The crystals of I were built up from monomeric complex molecules of MoO2 (C6H5CONHO)2, which are joined to one another by a system of hydrogen bonds to form a loose three-dimensional skeleton with large channel-like openings. The presence of solvent molecules in I (which were not detected by the analysis of the electron density) is indicated by the band of the stretching vibration of the carbonyl group nu(C=O) of propionic acid at nu = 1720 cm in the IR spectrum of I. The analysis of the derivatogram of I and the comparison of the values of the density of the crystal (calculated and experimental) indicate that the MoO2(BHA)2:PA ratio is equal to 1:2/3. An ordinary distorted octahedral environment of Mo(VI) consisting of oxygen atoms has been established. The geometric characteristics of the cis-molybdenyl grouping are as follows: Mo-O(1) = 1.701(4), Mo-O(2) = 1.679(6) A, and the OMoO angle equals 104.3(3). The magnitude of the effect of the influence of the double bonds in the two independent chelate rings is equal to 0.137 and 0.244 A. The complex molecules of MoO2 (BHA)2 are joined to one another by H bonds, which link the neighboring complexes in helical chains around 61 axes and bind these chains in a three-dimensional framework. The set of H bonds and the arrangement of the chelate rings and phenyl rings result in the formation of channels of types A and B. X-ray powder diffraction analysis showed that the channels of type A are randomly occupied by the molecules of propionic acid (PA).

Globally, terrestrial ecosystems have absorbed about 30% of anthropogenic greenhouse gas emissions over the period 2000-2007 and inter-hemispheric gradients indicate that a significant fraction of terrestrial carbon sequestration must be north of the Equator. We present a compilation of the CO{sub 2}, CO, CH{sub 4} and N{sub 2}O balances of Europe following a dual constraint approach in which (1) a land-based balance derived mainly from ecosystem carbon inventories and (2) a land-based balance derived from flux measurements are compared to (3) the atmospheric data-based balance derived from inversions constrained by measurements of atmospheric GHG (greenhouse gas) concentrations. Good agreement between the GHG balances based on fluxes (1294 {+-} 545 Tg C in CO{sub 2}-eq yr{sup -1}), inventories (1299 {+-} 200 Tg C in CO{sub 2}-eq yr{sup -1}) and inversions (1210 {+-} 405 Tg C in CO{sub 2}-eq yr{sup -1}) increases our confidence that the processes underlying the European GHG budget are well understood and reasonably sampled. However, the uncertainty remains large and largely lacks formal estimates. Given that European net land to atmosphere exchanges are determined by a few dominant fluxes, the uncertainty of these key components needs to be formally estimated before efforts could be made to reduce the overall uncertainty. The net land-to-atmosphere flux is a net source for CO{sub 2}, CO, CH{sub 4} and N{sub 2}O, because the anthropogenic emissions by far exceed the biogenic sink strength. The dual-constraint approach confirmed that the European biogenic sink removes as much as 205 {+-} 72 Tg C yr{sup -1} from fossil fuel burning from the atmosphere. However, This C is being sequestered in both terrestrial and inland aquatic ecosystems. If the C-cost for ecosystem management is taken into account, the net uptake of ecosystems is estimated to decrease by 45% but still indicates substantial C-sequestration. However, when the balance is extended from CO{sub 2} towards

Full-dimensional calculations of initial state-selected reaction probabilities on an accurate ab initio potential energy surface (PES) have been communicated recently [R. Welsch and U. Manthe, J. Chem. Phys. 141, 051102 (2014)]. These calculations use the quantum transition state concept, the multi-layer multi-configurational time-dependent Hartree approach, and graphics processing units to speed up the potential evaluation. Here further results of these calculations and an extended analysis are presented. State-selected reaction probabilities are given for many initial ro-vibrational states. The role of the vibrational states of the activated complex is analyzed in detail. It is found that rotationally cold methane mainly reacts via the ground state of the activated complex while rotationally excited methane mostly reacts via HĖHĖCH{sub 3}-bending excited states of the activated complex. Analyzing the different contributions to the reactivity of the vibrationally states of methane, a complex pattern is found. Comparison with initial state-selected reaction probabilities computed on the semi-empirical Jordan-Gilbert PES reveals the dependence of the results on the specific PES.

Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms,more¬†¬Ľ which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.¬ę¬†less

Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms, which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.

A five-dimensional potential energy surface (PES) for the interaction of a rigid methane molecule with a rigid nitrogen molecule was determined from quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the CCSD(T) level of theory was utilized to compute a total of 743 points on the PES. The interaction energies were calculated using basis sets of up to quadruple-zeta quality with bond functions and were extrapolated to the complete basis set limit. An analytical site-site potential function with nine sites for methane and five sites for nitrogen was fitted to the interaction energies. The PES was validated by calculating the cross second virial coefficient as well as the shear viscosity and binary diffusion coefficient in the dilute-gas limit for CH{sub 4}ĖN{sub 2} mixtures. An improved PES was obtained by adjusting a single parameter of the analytical potential function in such a way that quantitative agreement with the most accurate experimental values of the cross second virial coefficient was achieved. The transport property values obtained with the adjusted PES are in good agreement with the best experimental data.

Iron oxide (Fe{sub 2}O{sub 3}) or in its natural form (hematite) is a potential material to capture CO{sub 2} through the chemical-looping combustion (CLC) process. It is known that magnesium (Mg) is an effective methyl cleaving catalyst and as such it has been combined with hematite to assess any possible enhancement to the kinetic rate for the reduction of Fe{sub 2}O{sub 3} with methane. Therefore, in order to evaluate its effectiveness as a hematite additive, the behaviors of Mg-modified hematite samples (hematite Ė5% Mg(OH){sub 2}) have been analyzed with regard to assessing any enhancement to the kinetic rate process. The Mg-modified hematite was prepared by hydrothermal synthesis. The reactivity experiments were conducted in a thermogravimetric analyzer (TGA) using continuous stream of CH{sub 4} (5, 10, and 20%) at temperatures ranging from 700 to 825 {degrees}C over ten reduction cycles. The mass spectroscopy analysis of product gas indicated the presence of CO{sub 2}, H{sub 2}O, H{sub 2} and CO in the gaseous product. The kinetic data at reduction step obtained by isothermal experiments could be well fitted by two parallel rate equations. The modified hematite samples showed higher reactivity as compared to unmodified hematite samples during reduction at all investigated temperatures.

With the consideration of photon recycling effect, the efficiency limit of methylammonium lead iodide (CH{sub 3}NH{sub 3}PbI{sub 3}) perovskite solar cells is predicted by a detailed balance model. To obtain convincing predictions, both AM 1.5 spectrum of Sun and experimentally measured complex refractive index of perovskite material are employed in the detailed balance model. The roles of light trapping and angular restriction in improving the maximal output power of thin-film perovskite solar cells are also clarified. The efficiency limit of perovskite cells (without the angular restriction) is about 31%, which approaches to Shockley-Queisser limit (33%) achievable by gallium arsenide (GaAs) cells. Moreover, the Shockley-Queisser limit could be reached with a 200‚ÄČnm-thick perovskite solar cell, through integrating a wavelength-dependent angular-restriction design with a textured light-trapping structure. Additionally, the influence of the trap-assisted nonradiative recombination on the device efficiency is investigated. The work is fundamentally important to high-performance perovskite photovoltaics.

The complete spectrum of methanol (CH{sub 3}OH) has been characterized over a range of astrophysically significant temperatures in the 560.4-654.0 GHz spectral region. Absolute intensity calibration and analysis of 166 experimental spectra recorded over a slow 248-398 K temperature ramp provide a means for the simulation of the complete spectrum of methanol as a function of temperature. These results include contributions from v{sub t} = 3 and other higher states that are difficult to model via quantum mechanical (QM) techniques. They also contain contributions from the {sup 13}C isotopologue in terrestrial abundance. In contrast to our earlier work on semi-rigid species, such as ethyl cyanide and vinyl cyanide, significant intensity differences between these experimental values and those calculated by QM methods were found for many of the lines. Analysis of these differences shows the difficulty of the calculation of dipole matrix elements in the context of the internal rotation of the methanol molecule. These results are used to both provide catalogs in the usual line frequency, linestrength, and lower state energy format, as well as in a frequency point-by-point catalog that is particularly well suited for the characterization of blended lines.

For the last few years, Gaz de France has been interested in natural gas detection, which could become an additional service for its customers. Since these detectors would be linked to a shut-off valve, included in the new smart gas meter Dialogaz, they have to be reliable. That is why Gaz de France defined a protocol to evaluate sensors in terms of sensitivity to methane, selectivity to other gases and long-term stability. In the Gaz de France Research Centre laboratories, several commercialized sensors have already been tested among them the sensor CH-01, manufactured and distributed by New Cosmos Electric Co. Ltd, and distributed in Europe by Schlumberger Industries Gas Division, under the name CH-M.

Breaking of the carbon-hydrogen bond of benzene and pyridine is observed with (PNP)V(CH{sub 2}tBu){sub 2} (1), and in the case of benzene, the formation of an intermediate benzyne complex (C) is proposed, and indirect proof of its intermediacy is provided by identification of (PNP)VO({eta}{sup 2}-C{sub 6}H{sub 4}) in combination with DFT calculations.

Here, formaldehyde measurements from two independent instruments are compared with photochemical box model calculations. The measurements were made on the NOAA P-3 aircraft as part of the 1997 North Atlantic Regional Experiment (NARE 1997). After examining the possible reasons for the model-measurement discrepancy, we conclude that there are probably one or more additional unknown sources of CH2O in the North Atlantic troposphere.

Long, balanced electron and hole diffusion lengths greater than 100 nanometers in the polycrystalline organolead trihalide compound CH3NH3PbI3 are critical for highly efficient perovskite solar cells. We found that the diffusion lengths in CH3NH3PbI3 single crystals grown by a solution-growth method can exceed 175 micrometers under 1 sun (100 mW cm‚Äď2) illumination and exceed 3 millimeters under weak light for both electrons and holes. The internal quantum efficiencies approach 100% in 3-millimeter-thick single-crystal perovskite solar cells under weak light. These long diffusion lengths result from greater carrier mobility, longer lifetime, and much smaller trap densities in the single crystals thanmore¬†¬Ľ in polycrystalline thin films. As a result, the long carrier diffusion lengths enabled the use of CH3NH3PbI3 in radiation sensing and energy harvesting through the gammavoltaic effect, with an efficiency of 3.9% measured with an intense cesium-137 source.¬ę¬†less

[N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4} has been studied by X-ray powder diffraction patterns, differential scanning calorimetry (DSC), and impedance spectroscopy. The [N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4} hybrid compound is crystallized at room temperature (T ? 300?K) in the orthorhombic system with Pnma space group. Five phase transitions (T{sub 1}?=?255?K, T{sub 2}?=?282?K, T{sub 3}?=?302?K, T{sub 4}?=?320?K, and T{sub 5}?=?346?K) have been proved by DSC measurements. The electrical technique was measured in the 10{sup ?1}-10{sup 7}?Hz frequency range and 233Ė363?K temperature interval. The frequency dependence of alternative current (AC) conductivity is interpreted in terms of Jonscher's law. The AC electrical conduction in [N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4} is analyzed by different processes, which can be attributed to several models: the correlated barrier hopping model in phase I, the overlapping large polaron tunneling model in phase II, the quantum mechanical tunneling model in phase IV, and the non-overlapping small polaron tunneling model in phases III, V, and VI. The conduction mechanism is studied with the help of Elliot's theory, and the Elliot's parameters are determined.

The [N(CH{sub 3}){sub 3}H]{sub 2}CuCl{sub 4} single crystal has been analyzed by X-ray powder diffraction patterns, differential scanning calorimetry (DSC), and electrical impedance spectroscopy. [N(CH{sub 3}){sub 3}H]{sub 2}CuCl{sub 4} crystallizes at room temperature in the monoclinic system with P2{sub 1}/{sub C} space group. Three phase transitions at T{sub 1}?=?226?K, T{sub 2}?=?264?K, and T{sub 3}?=?297?K have been evidenced by DSC measurements. The electrical technique was measured in the 10{sup ?1}Ė10{sup 7}?Hz frequency range and 203Ė313?K temperature intervals. The frequency dependence of alternative current (AC) conductivity is interpreted in terms of Jonscher's law (developed). The AC electrical conduction in [N(CH{sub 3}){sub 3}H]{sub 2}CuCl{sub 4} compound is studied by two processes which can be attributed to a hopping transport mechanism: the correlated barrier hopping model in phases I, II, and III, the non-overlapping small polaron tunneling model in phase IV. The conduction mechanism is interpreted with the help of Elliot's theory, and the Elliot's parameters are found.

During the dissociative adsorption on a solid surface, the substrate usually participates in a passive manner to accommodate fragments produced upon the cleavage of the internal bond(s) of a (transient) molecular adsorbate. This simple picture, however, neglects the flexibility of surface atoms. Here, we report a Density Functional Theory study to revisit our early studies of the dissociative adsorption of CH{sub 3}X (X = Br and Cl) on Si(100). We have identified a new reaction pathway, which involves a flip of a silicon dimer; this new pathway agrees better with experiments. For our main exemplar of CH{sub 3}Br, insights have been gained using a simple model that involves a three-atom reactive center, Br-C-Si. When the silicon dimer flips, the interaction between C and Si in the Br-C-Si center is enhanced, evident in the increased energy-split of the frontier orbitals. We also examine how the dissociation dynamics of CH{sub 3}Br is altered on a heterodimer (Si-Al, Si-P, and Si-Ge) in a Si(100) surface. In each case, we conclude, on the basis of computed reaction pathways, that no heterodimer flipping is involved before the system transverses the transition state to dissociative adsorption.

Long, balanced electron and hole diffusion lengths greater than 100 nanometers in the polycrystalline organolead trihalide compound CH3NH3PbI3 are critical for highly efficient perovskite solar cells. We found that the diffusion lengths in CH3NH3PbI3 single crystals grown by a solution-growth method can exceed 175 micrometers under 1 sun (100 mW cm‚Äď2) illumination and exceed 3 millimeters under weak light for both electrons and holes. The internal quantum efficiencies approach 100% in 3-millimeter-thick single-crystal perovskite solar cells under weak light. These long diffusion lengths result from greater carrier mobility, longer lifetime, and much smaller trap densities in the single crystals thanmore¬†¬Ľin polycrystalline thin films. As a result, the long carrier diffusion lengths enabled the use of CH3NH3PbI3 in radiation sensing and energy harvesting through the gammavoltaic effect, with an efficiency of 3.9% measured with an intense cesium-137 source.¬ę¬†less

A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H2O, HDO, N2O and CH4 using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm-1 operating at similar to 7.8 mu m was scanned covering four neighboring absorption lines, for H2O at 1281.161 cm-1, HDO at 1281.455 cm-1, N2O at 1281.53 cm-1 and CH4 at 1281.61 cm-1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonic detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviationmore¬†¬Ľ analysis indicated that minimum detection limits of 1.77 ppmv for H2O, 3.92 ppbv for HDO, 1.43 ppbv for N2O, and 2.2 ppbv for CH4 were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. In conclusion, experimental measurements of ambient air are also reported.¬ę¬†less

The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the pplication." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the U.S. Department of Energy (DOE) or the Waste Isolation Pilot Plant (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations (CFR) ¬ß71.8. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required. In accordance with 10 CFR Part 71, certificate holders, packaging users, and contractors or subcontractors who use, design, fabricate, test, maintain, or modify the packaging shall post copies of (1) 10 CFR Part 21 regulations, (2) Section 206 of the Energy Reorganization Act of 1974, and (3) NRC Form 3, Notice to Employees. These documents must be posted in a conspicuous location where the activities subject to these regulations are conducted. This document provides the instructions to be followed to operate, maintain, and test the TRUPACT-II and HalfPACT packaging. The intent of these instructions is to standardize operations. All users will follow these instructions or equivalent instructions that assure operations are safe and meet the requirements of the SARPs.

The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the U.S. Department of Energy (DOE) or the Waste Isolation Pilot Plant (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations (CFR) ¬ß71.8. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required.In accordance with 10 CFR Part 71, certificate holders, packaging users, and contractors or subcontractors who use, design, fabricate, test, maintain, or modify the packaging shall post copies of (1) 10 CFR Part 21 regulations, (2) Section 206 of the Energy Reorganization Act of 1974, and (3) NRC Form 3, Notice to Employees. These documents must be posted in a conspicuous location where the activities subject to these regulations are conducted.

The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package TransporterModel II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the U.S. Department of Energy (DOE) or the Waste Isolation Pilot Plant| (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations(CFR) ¬ß71.8. Any time a user suspects or has indications that the conditions ofapproval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required.In accordance with 10 CFR Part 71, certificate holders, packaging users, and contractors or subcontractors who use, design, fabricate, test, maintain, or modify the packaging shall post copies of (1) 10 CFR Part 21 regulations, (2) Section 206 of the Energy Reorganization Act of 1974, and (3) NRC Form 3, Notice to Employees. These documents must be posted in a conspicuous location where the activities subject to these regulations are conducted.

The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the Waste Isolation Pilot Plant (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations (CFR) ¬ß71.8. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required.

The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the U.S. Department of Energy (DOE) or the Waste Isolation Pilot Plant (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations (CFR) ¬ß71.8. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required. In accordance with 10 CFR Part 71, certificate holders, packaging users, and contractors or subcontractors who use, design, fabricate, test, maintain, or modify the packaging shall post copies of (1) 10 CFR Part 21 regulations, (2) Section 206 of the Energy Reorganization Act of 1974, and (3) NRC Form 3, Notice to Employees. These documents must be posted in a conspicuous location where the activities subject to these regulations are conducted. This document provides the instructions to be followed to operate, maintain, and test the TRUPACT-II and HalfPACT packaging. The intent of these instructions is to standardize operations. All users will follow these instructions or equivalent instructions that assure operations are safe and meet the requirements of the SARPs.

The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: ''each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application.'' They further state: ''each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application.'' Chapter 9.0 of the SARP charges the WIPP management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with 10 CFR 71.11. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. CBFO will evaluate the issue and notify the NRC if required. This document provides the instructions to be followed to operate, maintain, and test the TRUPACT-II and HalfPACT packaging. The intent of these instructions is to standardize operations. All users will follow these instructions or equivalent instructions that assure operations are safe and meet the requirements of the SARPs.

The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT Shipping Package, and directly related components. This document complies with the minimum requirements as specified in TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event there is a conflict between this document and the SARP or C of C, the SARP and/or C of C shall govern. C of Cs state: ''each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application.'' They further state: ''each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application.'' Chapter 9.0 of the SAR P charges the WIPP Management and Operation (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with 10 CFR 71.11. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. CBFO will evaluate the issue and notify the NRC if required. This document details the instructions to be followed to operate, maintain, and test the TRUPACT-II and HalfPACT packaging. The intent of these instructions is to standardize these operations. All users will follow these instructions or equivalent instructions that assure operations are safe and meet the requirements of the SARPs.

Several popular force fields, namely, CHARMM, AMBER, OPLS-AA, and MM3, have been tested for their ability to reproduce highly accurate quantum mechani- cal potential energy curves for noncovalent interactions in the benzene dimer, the benzene-CH4 complex, and the benzene-H2S complex. All of the force fields are semi-quantitatively correct, but none of them is consistently reliable quantitatively. Re-optimization of Lennard-Jones parameters and symmetry-adapted perturbation theory analysis for the benzene dimer suggests that better agreement cannot be expected unless more flexible functional forms (particularly for the electrostatic contributions)are employed for the empirical force fields.

The initial reaction of HFe/sub 4/(CH)(CO)/sub 12/ with partially dehydroxylated alumina produces (HFe/sub 4/(C)(CO)/sub 12/)/sup -/, which is bound to the surface. Evolution of CO occurs slowly by extensive loss of CO from a small number of cluster molecules. This process leads to the coexistence of intact (HFe/sub 4/(C)(CO)/sub 12/)/sup -/ plus an iron or iron carbide like species. In keeping with this interpretation, the supported material displays activities for the reduction of Co and the hydrogenation of benzene and product distributions that are typical of iron metal.

Theoretical investigation of structural and electronic properties is presented for the rod-like oligomers R{sub 3}-[MRNH]{sub 3n}-H{sub 3} and [RMNH]{sub n+1} (M=Ga,Al,In R=H,CH{sub 3}) of different lengths. Electronic structures of the oligomers with and without substitutions of Ga atoms with Al or In were studied at DFT level of theory. Clusters up to 8‚ÄÖnm of length were considered. A type of terminal groups of the oligomers is found to have a dominant influence on their electronic properties.

Motivated by a recent crossed-beam experiment on the title reaction reported by Pan and Liu [J. Chem. Phys. 140, 191101 (2014)], a detailed dynamics study was performed at three collision energies using quasiclassical trajectory (QCT) calculations based on a full-dimensional potential energy surface recently developed by our group (PES-2014). Although theory/experiment agreement is not yet quantitative, in general the theoretical results reproduce the experimental evidence: the vibrational branching ratio of OH(v = 1)/OH(v = 0) is ‚ąľ0.8/0.2, excitation of the antisymmetric CH stretching mode in methane increases reactivity by factor 2.28‚Äď1.50, although an equivalent amount as translational energy is more efficient in promoting the reaction and, finally, product angular distribution shifts from backward in the CH{sub 4}(őĹ = 0) ground-state to sideways when the antisymmetric CH stretching mode is excited. These results give confidence to the PES-2014 surface, depend on the quantization procedure used, are comparable with recent QCT calculations or improve previous theoretical studies using a different surface, and demonstrate the utility of the theory/experiment collaboration.

Understanding and controlling bond-breaking sequences of oxygenates on transition metal catalysts can greatly impact the utilization of biomass feedstocks for fuels and chemicals. The decomposition of ethylene glycol, as the simplest representative of biomass-derived polyols, was studied via density functional theory (DFT) calculations to identify the differences in reaction pathways between Pt and the more active Ni/Pt bimetallic catalyst. Comparison of the computed transition states indicated three potentially feasible paths from ethylene glycol to C1 oxygenated adsorbates on Pt. While not important on Pt, the pathway to 1,2-dioxyethylene (OCH?CH?O) is favored energetically on the Ni/Pt catalyst. Temperature-programmed desorption (TPD) experiments were conducted with deuterated ethylene glycols for comparison with DFT results. These experiments confirmed that decomposition of ethylene glycol on Pt proceeds via initial OĖH bond cleavage, followed by CĖH and the second OĖH bond cleavages, whereas on the Ni/Pt surface, both OĖH bonds are cleaved initially. The results are consistent with vibrational spectra and indicate that tuning of the catalyst surface can selectively control bond breaking. Finally, the significant mechanistic differences in decomposition of polyols compared to that of monoalcohols and hydrocarbons serve to identify general trends in bond scission sequences.

Role of ďOĒ defects in sensing pollutant with nanostructured SnO{sub 2} is not well understood, especially at low temperatures. SnO{sub 2} nanoparticles were grown by soft chemistry route followed by subsequent annealing treatment under specific conditions. Nanowires were grown by chemical vapor deposition technique. A systematic photoluminescence (PL) investigation of ďOĒ defects in SnO{sub 2} nanostructures revealed a strong correlation between shallow donors created by the in-plane and the bridging ďOĒ vacancies and gas sensing at low temperatures. These SnO{sub 2} nanostructures detected methane (CH{sub 4}), a reducing and green house gas at a low temperature of 50?įC. Response of CH{sub 4} was found to be strongly dependent on surface defect in comparison to surface to volume ratio. Control over ďOĒ vacancies during the synthesis of SnO{sub 2} nanomaterials, as supported by X-ray photoelectron spectroscopy and subsequent elucidation for low temperature sensing are demonstrated.

By forming a highly stable Al{sub 2}O{sub 3} gate oxide on a C-H bonded channel of diamond, high-temperature, and high-voltage metal-oxide-semiconductor field-effect transistor (MOSFET) has been realized. From room temperature to 400‚ÄČ¬įC (673‚ÄČK), the variation of maximum drain-current is within 30% at a given gate bias. The maximum breakdown voltage (V{sub B}) of the MOSFET without a field plate is 600‚ÄČV at a gate-drain distance (L{sub GD}) of 7 őľm. We fabricated some MOSFETs for which V{sub B}/L{sub GD}‚ÄČ>‚ÄČ100‚ÄČV/őľm. These values are comparable to those of lateral SiC or GaN FETs. The Al{sub 2}O{sub 3} was deposited on the C-H surface by atomic layer deposition (ALD) at 450‚ÄČ¬įC using H{sub 2}O as an oxidant. The ALD at relatively high temperature results in stable p-type conduction and FET operation at 400‚ÄČ¬įC in vacuum. The drain current density and transconductance normalized by the gate width are almost constant from room temperature to 400‚ÄČ¬įC in vacuum and are about 10 times higher than those of boron-doped diamond FETs.

A global many-body expansion potential energy surface is reported for the electronic ground state of CH{sub 2}{sup +} by fitting high level ab initio energies calculated at the multireference configuration interaction level with the aug-cc-pV6Z basis set. The topographical features of the new global potential energy surface are examined in detail and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. In turn, in order to validate the potential energy surface, a test theoretical study of the reaction CH{sup +}(X{sup 1}ő£{sup +})+H({sup 2}S)‚ÜíC{sup +}({sup 2}P)+H{sub 2}(X{sup 1}ő£{sub g}{sup +}) has been carried out with the method of time dependent wavepacket on the title potential energy surface. The total integral cross sections and the rate coefficients have been calculated; the results determined that the new potential energy surface can both be recommended for dynamics studies of any type and as building blocks for constructing the potential energy surfaces of larger C{sup +}/H containing systems.

InSb is an important material for optoelectronic devices. Most InSb devices are currently wet etched, and the etching geometries are limited due to the isotropic nature of wet etching. Inductively coupled plasma (ICP)-reactive ion etching (RIE) is a more desirable alternative because it offers a means of producing small anisotropic structures especially needed in large format infrared focal plane arrays. This work describes the novel use of ICP-RIE for fabricating InSb mesas with CH{sub 4}/H{sub 2}/Ar plasma and presents the influences of the process parameters on the etch rate and surface morphology. The parameters investigated include bias radio frequency power (50-250 W), %CH{sub 4} in H{sub 2} (10-50), argon (Ar) partial pressure (0-0.3 Pa with total pressure of 1.0 Pa), and total pressure (0.35-4 Pa). With the process parameters optimized in this investigated ranges, good etching results have been achieved with etch rates up to 80 nm/min, and etch features with sidewall angles of about 80 degree sign , the etched surface is as smooth as before the RIE process.

One of the best ways to increase the diamond growth rate is to couple high microwave power to the plasma. Indeed, increasing the power density leads to increase gas temperature the atomic hydrogen density in the plasma bulk, and to produce more hydrogen and methyl at the diamond surface. Experimental and numerical approaches were used to study the microwave plasma under high power densities conditions. Gas temperature was measured by optical emission spectroscopy and H-atom density using actinometry. CH{sub 3}-radical density was obtained using a 1D model that describes temperatures and plasma composition from the substrate to the top of the reactor. The results show that gas temperature in the plasma bulk, atomic hydrogen, and methyl densities at the diamond surface highly increase with the power density. As a consequence, measurements have shown that diamond growth rate also increases. At very high power density, we measured a growth rate of 40??m/h with an H-atom density of 5 ◊ 10{sup 17} cm{sup ?3} which corresponds to a H{sub 2} dissociation rate higher than 50%. Finally, we have shown that the growth rate can be framed between a lower and an upper limit as a function depending only on the maximum of H-atom density measured or calculated in the plasma bulk. The results also demonstrated that increasing fresh CH{sub 4} by an appropriate injection into the boundary layer is a potential way to increase the diamond growth rates.

We report a permutationally invariant global potential energy surface (PES) for the H + CH{sub 4} system based on ‚ąľ63 000 data points calculated at a high ab initio level (UCCSD(T)-F12a/AVTZ) using the recently proposed permutation invariant polynomial-neural network method. The small fitting error (5.1 meV) indicates a faithful representation of the ab initio points over a large configuration space. The rate coefficients calculated on the PES using tunneling corrected transition-state theory and quasi-classical trajectory are found to agree well with the available experimental and previous quantum dynamical results. The calculated total reaction probabilities (J{sub tot} = 0) including the abstraction and exchange channels using the new potential by a reduced dimensional quantum dynamic method are essentially the same as those on the Xu-Chen-Zhang PES [Chin. J. Chem. Phys. 27, 373 (2014)].

Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH3NH3PbBr3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4¬Ī0.1 103 cm s-1, B2‚Äď3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggests that the planar grain size for the perovskite thin films should be larger thanB30 mm to avoid the influence of surface recombination on the effective carrier lifetime.

Interactions between CH4, COOH, NH3, OH, SH and armchair (n,n)(n=4,7,14) and zigzag (n,0)(n=7,12,25) single-walled carbon nanotubes (SWCNTs) have been systematically investigated within the framework of dispersion-corrected density functional theory (DFT-D2). Endohedral and exohedral molecular adsorption on SWCNT walls is energetically unfavorable or weak, despite the use of C6/r6 pairwise London-dispersion corrections. The effects of pore size and chirality on the molecule/SWCNTs interaction were also assessed. Furthermore, chemisorption of COOH, NH3, OH and SH at SWCNT edge sites was examined using a H-capped (7,0) SWCNT fragment and its impact on electrophilic, nucleophilic and radical attacks was predicted by means of Fukuimore¬†¬Ľ functions.¬ę¬†less

We report the observation of self-doping in perovskite. CH{sub 3}NH{sub 3}PbI{sub 3} was found to be either n- or p-doped by changing the ratio of methylammonium halide (MAI) and lead iodine (PbI{sub 2}) which are the two precursors for perovskite formation. MAI-rich and PbI{sub 2}-rich perovskite films are p and n self-doped, respectively. Thermal annealing can convert the p-type perovskite to n-type by removing MAI. The carrier concentration varied as much as six orders of magnitude. A clear correlation between doping level and device performance was also observed.

This work aims to simplify multi-dimensional femtosecond transient absorption microscopy (TAM) data into decay associated amplitude maps that describe the spatial distributions of dynamical processes occurring on various characteristic timescales. Application of this method to TAM data obtained from a model methyl-ammonium lead iodide (CH3NH3PbI3) perovskite thin film allows us to simplify the dataset consisting of a 68 time-resolved images into 4 decay associated amplitude maps. These maps provide a simple means to visualize the complex electronic excited-state dynamics in this system by separating distinct dynamical processes evolving on characteristic timescales into individual spatial images. This approach provides new insightmore¬†¬Ľ into subtle aspects of ultrafast relaxation dynamics associated with excitons and charge carriers in the perovskite thin film, which have recently been found to coexist at spatially distinct locations.¬ę¬†less

The large photocurrent hysteresis observed in many organometal trihalide perovskite solar cells has become a major hindrance impairing the ultimate performance and stability of these devices, while its origin was unknown. Here we demonstrate the trap states on the surface and grain boundaries of the perovskite materials to be the origin of photocurrent hysteresis and that the fullerene layers deposited on perovskites can effectively passivate these charge trap states and eliminate the notorious photocurrent hysteresis. Fullerenes deposited on the top of the perovskites reduce the trap density by two orders of magnitude and double the power conversion efficiency of CH3NH3PbI3more¬†¬Ľ solar cells. As a result, the elucidation of the origin of photocurrent hysteresis and its elimination by trap passivation in perovskite solar cells provides important directions for future enhancements to device efficiency.¬ę¬†less

The reaction of the cyano radical (CN) with methane was studied by time-resolved infrared absorption spectroscopy by monitoring individual rovibrational states of the HCN and CH{sub 3} products. The initial vibrational level distribution of the bendless vibrational levels of HCN({ital v}{sub 1},0,{ital v}{sub 3}) was determined by plotting the time dependence of the fractional population of a vibrational level and extrapolating these curves to the origin of time. About 20{percent} of the HCN products were observed to be initially produced in the HCN({ital v}{sub 1},0,{ital v}{sub 3}) vibrational levels, with {ital v}{sub 1} and {ital v}{sub 3}=0,1,2. The CN radical was created by laser photolysis of three different precursors. Each photolyte provided a different initial vibrational level distribution of CN; however, similar initial HCN({ital v}{sub 1},0,{ital v}{sub 3}) vibrational level distributions were obtained independent of the CN radical precursor. This may indicate that the CN radical does not act as a spectator bond during the course of a reactive encounter for this system. The time dependence of the CH{sub 3} (000{sup 0}0) ground state was also followed using time-resolved infrared absorption spectroscopy. Preliminary data indicates that a large fraction, if not all, the CH{sub 3} radicals are produced in their ground state in the title reaction. {copyright} {ital 1996 American Institute of Physics.}

The X-ray powder diffraction pattern shows that at room temperature, [N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4} is crystallized in the orthorhombic system with Pnma space group. The phase transitions at T{sub 1}‚ÄČ=‚ÄČ255‚ÄČK, T{sub 2}‚ÄČ=‚ÄČ282‚ÄČK, T{sub 3}‚ÄČ=‚ÄČ302‚ÄČK, T{sub 4}‚ÄČ=‚ÄČ320‚ÄČK, and T{sub 5}‚ÄČ=‚ÄČ346‚ÄČK have been confirmed by the differential scanning calorimetry. The electrical technique was measured in the 10{sup ‚ąí1}‚Äď10{sup 7‚ÄČ}Hz frequency range and 233‚Äď363‚ÄČK temperature intervals. The temperature dependence of the dielectric constant at different temperatures proved that this compound is ferroelectric below 282‚ÄČK. Besides, [N(CH{sub 3}){sub 3‚ÄČ}H]{sub 2}ZnCl{sub 4} shows classical ferroelectric behaviour near curie temperature. In order to characterize the phase transitions, Raman spectra have been recorded in the temperature range of 233‚Äď383‚ÄČK and the frequency range related to the internal and external vibrations of the cations and anions (90‚Äď4000‚ÄČcm{sup ‚ąí1}). The temperature dependence of the Raman line shifts őĹ and the half-width őĒőĹ detects all phase transitions and confirms their nature, especially at 282‚ÄČK that corresponds to the ferroelectric-paraelectric phase transition.

This project focuses on the systematic study of CH4-CO2-H2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.

Ab initio quantum mechanical techniques, including the self-consistent field (SCF), single and double excitation configuration interaction (CISD), single and double excitation double cluster (CCSD), and the single, double and perturbative triple excitation coupled cluster [CCSD(T)] methods have been applied to study the HCCO(a {sup 4}A{open_quotes}) energy hypersurface. Rate constant measurements suggest an attractive potential for the reaction of CH(a {sup 4}{sigma}{sup -}) with CO, and a vanishingly small energy barrier is predicted here in the CH(a {sup 4}{sigma}{sup -}) + CO reaction channel. The {sup 4}A{open_quotes} state of HCCO is predicted to be bound by about 30 kcal/mol with respect to separated CH(a {sup 4}{sigma}{sup -}) + CO. The authors propose that a spin-forbidden electronic deactivation of CH(a {sup 4}{sigma}{sup -}) might occur through through an intersystem crossing involving the {sup 4}A{open_quotes} state of HCCO. The energetics and the geometries of the reactants and products on both quartet and doublet energy surfaces are presented. The relationship between this research and experimental combustion chemistry has been explored.

CH{sub 4} and C{sub 2}H{sub 2} molecules (and their interconversion) in hydrocarbon/rare gas/H{sub 2} gas mixtures in a microwave reactor used for plasma enhanced diamond chemical vapor deposition (CVD) have been investigated by line-of-sight infrared absorption spectroscopy in the wavenumber range of 1276.5-1273.1 cm{sup -1} using a quantum cascade laser spectrometer. Parameters explored include process conditions [pressure, input power, source hydrocarbon, rare gas (Ar or Ne), input gas mixing ratio], height (z) above the substrate, and time (t) after addition of hydrocarbon to a pre-existing Ar/H{sub 2} plasma. The line integrated absorptions so obtained have been converted to species number densities by reference to the companion two-dimensional (r,z) modeling of the CVD reactor described in Mankelevich et al. [J. Appl. Phys. 104, 113304 (2008)]. The gas temperature distribution within the reactor ensures that the measured absorptions are dominated by CH{sub 4} and C{sub 2}H{sub 2} molecules in the cool periphery of the reactor. Nonetheless, the measurements prove to be of enormous value in testing, tensioning, and confirming the model predictions. Under standard process conditions, the study confirms that all hydrocarbon source gases investigated (methane, acetylene, ethane, propyne, propane, and butane) are converted into a mixture dominated by CH{sub 4} and C{sub 2}H{sub 2}. The interconversion between these two species is highly dependent on the local gas temperature and the H atom number density, and thus on position within the reactor. CH{sub 4}->C{sub 2}H{sub 2} conversion occurs most efficiently in an annular shell around the central plasma (characterized by 1400CH{sub 4} is favored in the more distant regions where T{sub gas}<1400 K. Analysis of the multistep interconversion mechanism reveals substantial net consumption of H atoms accompanying the CH{sub 4}->C{sub 2}H{sub 2

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

11 by ASME Proceedings of the ASME 30th International Conference on Ocean, Offshore and Arctic Engineering OMAE2011 June 19-24, 20111, Rotterdam, the Netherland OMAE2011-50063 STRUCTURAL DESIGN OF A HORIZONTAL-AXIS TIDAL CURRENT TURBINE COMPOSITE BLADE ABSTRACT This paper describes the structural design of a tidal turbine composite blade. The structural design is preceded by two steps: hydrodynamic design and determination of extreme loads. The hydrodynamic design provides the blade external

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

We have demonstrated the performance of inverted CH{sub 3}NH{sub 3}PbI{sub 3} perovskite-based solar cells (SCs) with a room temperature (RT) sputtered ZnO electron transport layer by adding fullerene (C{sub 60}) interlayer. ZnO exhibits a better matched conduction band level with perovskite and Al work function and around energy offset of 2.2‚ÄČeV between highest occupied molecular orbital level of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite and valance band level of ZnO. However, the CH{sub 3}NH{sub 3}PbI{sub 3} perovskite layer will be damaged during direct RT sputtering deposition of ZnO. Therefore, the C{sub 60} interlayer having matched conduction band level with ZnO and CH{sub 3}NH{sub 3}PbI{sub 3} perovskite added between the CH{sub 3}NH{sub 3}PbI{sub 3} perovskite and RT sputtered ZnO layers for protection prevents sputtering damages on the CH{sub 3}NH{sub 3}PbI{sub 3} perovskite layer. The short-circuit current density (J{sub SC}, 19.41‚ÄČmA/cm{sup 2}) and open circuit voltage (V{sub OC}, 0.91‚ÄČV) of the SCs with glass/ITO/poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS)/perovskite/C{sub 60}/RT sputtered ZnO/Al structure is higher than the J{sub SC} (16.23‚ÄČmA/cm{sup 2}) and V{sub OC} (0.90‚ÄČV) of the reference SC with glass/ITO/PEDOT:PSS/perovskite/C{sub 60}/bathocuproine (BCP)/Al structure. Although the SCs with the former structure has a lower fill factor (FF%) than the SCs with the latter structure, its conversion efficiency ő∑% (10.93%) is higher than that (10.6%) of the latter.

A high-pressure x-ray diffraction study of nanocrystalline pentaerythritol tetranitrate, C(CH{sub 2}ONO{sub 2}){sub 4}, (PETN), has been performed in a diamond-anvil cell at ambient temperature using synchrotron radiation. Pressure-induced alterations in the profiles of the diffraction lines, including their positions, widths and intensities were followed up to 30 GPa in a compressino cycle. The spectral changes in the diffraction patterns at low pressures indicated continuous densification of the tetragonal structure (space group P{bar 4}2{sub 1}c). The diffraction patterns confirmed that PETN compressed from ambient pressure to 7.4 GPa by 17%. At 8.2 GPa and above, several new diffraction lines appeared in the patterns. These lines suggest that the lattice undergoes an incomplete stress-induced structural transformation from the tetragonal to an orthorhombic structure (most probably space group P2{sub 1}22{sub 1}). The mixture of both structures appeared to persist to 30 GPa. The progressive broadening of the diffraction lines as the pressure increased beyond 10 GPa is attributed to the combined diffraction lines of a mixture of two coexisting PETN phases and inhomogeneous pressure distribution within the sample.

We have compiled a greater than 10,000 CH-TRU waste drum data base from seven DOE sites which have utilized such multiple NDA measurements within the past few years. Most of these nondestructive assay (NDA) technique assay result comparisons have been performed on well-characterized, segregated waste categories such as cemented sludges, combustibles, metals, graphite residues, glasses, etc., with well-known plutonium isotopic compositions. Waste segregation and categorization practices vary from one DOE site to another. Perhaps the most systematic approach has been in use for several years at the Rocky Flats Plant (RFP), operated by Rockwell International, and located near Golden, Colorado. Most of the drum assays in our data base result from assays of RFP wastes, with comparisons available between the original RFP assays and PAN assays performed independently at the Idaho National Engineering Laboratory (INEL) Solid Waste Examination Pilot Plant (SWEPP) facility. Most of the RFP assays were performed with hyperpure germanium (HPGe)-based SGS assay units. However, at least one very important waste category, processed first-stage sludges, is assayed at RFP using a sludge batch-sampling procedure, prior to filling of the waste drums. 5 refs., 5 figs.

The spectrum of methanol (CH{sub 3}OH) has been characterized between 214.6 and 265.4 GHz for astrophysically significant temperatures. Four hundred and eighty-six spectra with absolute intensity calibration recorded between 240 and 389 K provided a means for the calculation of the complete experimental spectrum (CES) of methanol as a function of temperature. The CES includes contributions from v{sub t} = 3 and other higher states that are difficult to model quantum mechanically (QM). It also includes the spectrum of the {sup 13}C isotopologue in terrestrial abundance. In general the QM models provide frequencies that are within 1 MHz of their experimental values, but there are several outliers that differ by tens of MHz. As in our recent work on methanol in the 560-654 GHz region, significant intensity differences between our experimental intensities and cataloged values were found. In this work these differences are explored in the context of several QM analyses. The experimental results presented here are analyzed to provide a frequency point-by-point catalog that is well suited for the simulation of crowded and overlapped spectra. Additionally, a catalog in the usual line frequency, line strength, and lower state energy format is provided.

We report the first subarcsecond (0.''65 x 0.''51) image of the dimethyl ether molecule, (CH{sub 3}){sub 2}O, toward the Orion Kleinmann-Low nebula. The observations were carried at 43.4 GHz with the Expanded Very Large Array (EVLA). The distribution of the lower energy transition 6{sub 1,5}-6{sub 0,6}, EE (E {sub u} = 21 K) mapped in this study is in excellent agreement with the published dimethyl ether emission maps imaged with a lower resolution. The main emission peaks are observed toward the Compact Ridge and Hot Core southwest components, at the northern parts of the Compact Ridge and in an intermediate position between the Compact Ridge and the Hot Core. A notable result is that the distribution of dimethyl ether is very similar to that of another important larger O-bearing species, the methyl formate (HCOOCH{sub 3}), imaged at a lower resolution. Our study shows that higher spectral resolution (WIDAR correlator) and increased spectral coverage provided by the EVLA offer new possibilities for imaging complex molecular species. The sensitivity improvement and the other EVLA improvements make this instrument well suited for high sensitivity, high angular resolution, and molecular line imaging.

Long, balanced electron and hole diffusion lengths greater than 100 nanometers in the polycrystalline organolead trihalide compound CH3NH3PbI3 are critical for highly efficient perovskite solar cells. We found that the diffusion lengths in CH3NH3PbI3 single crystals grown by a solution-growth method can exceed 175 micrometers under 1 sun (100 mW cm‚Äď2) illumination and exceed 3 millimeters under weak light for both electrons and holes. The internal quantum efficiencies approach 100% in 3-millimeter-thick single-crystal perovskite solar cells under weak light. These long diffusion lengths result from greater carrier mobility, longer lifetime, and much smaller trap densities in the single crystals than in polycrystalline thin films. As a result, the long carrier diffusion lengths enabled the use of CH3NH3PbI3 in radiation sensing and energy harvesting through the gammavoltaic effect, with an efficiency of 3.9% measured with an intense cesium-137 source.

0 0 Conventional Facilities TECHNICAL SYNOPSIS The LCLS takes advantage of the existing infrastructure at SLAC. It uses the last third of the existing 3 km linac including the existing enclosure and utilities. A new injector will be installed at sector 20 in the Off-Axis Injector Tunnel. This branch tunnel was constructed as part of the original construction at SLAC in the 1960s for just such an injector. The existing linac equipment including the klystrons and modulators will be used. The

Large single crystals of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}∑2H{sub 2}O with dimensions up to 40◊40◊30 mm{sup 3} were grown from aqueous solutions. The elastic and piezoelastic coefficients were derived from ultrasonic resonance frequencies and their shifts upon variation of pressure, respectively, using the plate-resonance technique. Additionally, the coefficients of thermal expansion were determined between 95 K and 305 K by dilatometry. The elastic behaviour at ambient conditions is dominated by the 2-dimensional network of strong hydrogen bonds within the (001) plane leading to a corresponding pseudo-tetragonal anisotropy of the longitudinal elastic stiffness. The variation of elastic properties with pressure, however, as well as the thermal expansion shows strong deviations from the pseudo-tetragonal symmetry. These deviations are probably correlated with tilts of the elongated tri-nuclear betaineĖCuCl{sub 2}Ėwater complexes. Neither the thermal expansion nor the specific heat capacity gives any hint on a phase transition in the investigated temperature range. - Graphical abstract: Single crystal of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}∑2H{sub 2}O. - Highlights: ē Large single crystals (40 ◊40 ◊30 mm{sup 3}) of [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}∑2H{sub 2}O were grown. ē The elastic and piezoelastic coefficients were derived from ultrasonic resonance frequencies. ē Thermal expansion (95 KĖ305 K) and heat capacity (113 KĖ323 K) were determined. ē The orthorhombic structure shows pseudo-tetragonal elastic anisotropy at ambient conditions. ē The crystal structure is stable in the investigated range (1Ė1600 bar, 95Ė303 K)

The electronic absorption spectrum of diiodomethane in the 30?000Ė95?000 cm{sup ?1} region is investigated using synchrotron radiation; the spectrum in the 50?000Ė66?500 cm{sup ?1} region is reported for the first time. The absorption bands in the 30?000Ė50?000 cm{sup ?1} region are attributed to valence transitions, while the vacuum ultraviolet (VUV) spectrum (50?000Ė95?000 cm{sup ?1}) is dominated by several Rydberg series converging to the first four ionization potentials of CH{sub 2}I{sub 2} at 9.46, 9.76, 10.21, and 10.56 eV corresponding to the removal of an electron from the outermost 3b{sub 2}, 2b{sub 1}, 1a{sub 2}, and 4a{sub 1} non-bonding orbitals, respectively. Rydberg series of ns, np, and nd type converging to each of the four ionization potentials are assigned based on a quantum defect analysis. Time dependent density functional theory calculations of excited states support the analysis and help in interpretation of the Rydberg and valence nature of observed transitions. Density functional theory calculations of the neutral and ionic ground state geometries and vibrational frequencies are used to assign the observed vibronic structure. Vibronic features accompanying the Rydberg series are mainly due to excitation of the C-I symmetric stretch (?{sub 3}) and CH{sub 2} wag (?{sub 8}) modes, with smaller contributions from the C-H symmetric stretch (?{sub 1}). UV absorption bands are assigned to low lying valence states 1{sup 1}B{sub 2}, 1{sup 1}B{sub 1}, 2{sup 1}A{sub 1}, 3{sup 1}A{sub 1}, 2{sup 1}B{sub 1}, and 2{sup 1}B{sub 2} and the unusually high underlying intensity in parts of the VUV spectrum is attributed to valence states with high oscillator strength. This is the first report of a comprehensive Rydberg series and vibronic analysis of the VUV absorption spectrum of CH{sub 2}I{sub 2} in the 50?000Ė85?000 cm{sup ?1} region. The VUV absorption spectrum of CD{sub 2}I{sub 2} which serves to verify and consolidate spectral assignments is also

Searches are presented for heavy scalar (H) and pseudoscalar (A) Higgs bosons posited in the two doublet model (2HDM) extensions of the standard model (SM). These searches are based on a data sample of pp collisions collected with the CMS experiment at the LHC at a center-of-mass energy of ?s = 8 TeV and corresponding to an integrated luminosity of 19.5 fb -1. The decays H ? hh and A ? Zh, where h denotes an SM-like Higgs boson, lead to events with three or more isolated charged leptons or with a photon pair accompanied by one or more isolated leptons. The search results are presented in terms of the H and A production cross sections times branching fractions and are further interpreted in terms of 2HDM parameters. We place 95% CL cross section upper limits of approximately 7 pb on ?? for H ? hh and 2 pb for A ? Zh. Also presented are the results of a search for the rare decay of the top quark that results in a charm quark and an SM Higgs boson, t ? ch, the existence of which would indicate a nonzero flavor-changing Yukawa coupling of the top quark to the Higgs boson. We place a 95% CL upper limit of 0.56% on B(t ? ch).

State-to-state rate constants for the title reaction are calculated using the electronic ground state potential energy surface and an accurate quantum wave-packet method. The calculations are performed for H{sub 2} in different rovibrational states, v = 0, 1 and J = 0 and 1. The simulated reaction cross section for v = 0 shows a rather good agreement with the experimental results of Gerlich et al., both with a threshold of 0.36 eV and within the experimental error of 20%. The total reaction rate coefficients simulated for v = 1 are two times smaller than those estimated by Hierl et al. from cross sections measured at different temperatures and neglecting the contribution from v > 1 with an uncertainty factor of two. Thus, part of the disagreement is attributed to the contributions of v > 1. The computed state-to-state rate coefficients are used in our radiative transfer model code applied to the conditions of the Orion Bar photodissociation region, and leads to an increase of the line fluxes of high-J lines of CH{sup +}. This result partially explains the discrepancies previously found with measurements and demonstrates that CH{sup +} excitation is mostly driven by chemical pumping.

We obtained infrared spectra of Comet 21P/Giacobini-Zinner (hereafter 21P/GZ) using NIRSPEC at Keck II on UT 2005 June 3, approximately one month before perihelion, that simultaneously sampled H{sub 2}O, C{sub 2}H{sub 6}, and CH{sub 3}OH. Our production rate for H{sub 2}O (3.885 {+-} 0.074 Multiplication-Sign 10{sup 28} molecules s{sup -1}) was consistent with that measured during other apparitions of 21P/GZ as retrieved from optical, infrared, and radio observations. Our analysis also provided values for rotational temperature (T {sub rot} = 51 {+-} 3 K) and the abundance ratio of ortho and para spin populations for water (OPR = 2.99 {+-} 0.23, implying a spin temperature exceeding 50 K). Six Q-branches in the {nu}{sub 7} band of C{sub 2}H{sub 6} provided a production rate (5.27 {+-} 0.90 Multiplication-Sign 10{sup 25} s{sup -1}) that corresponded to an abundance ratio of 0.136 {+-} 0.023 Multiplication-Sign 10{sup -2} relative to H{sub 2}O, confirming the previously reported strong depletion of C{sub 2}H{sub 6} from IR observations during the 1998 apparition, and in qualitative agreement with the depletion of C{sub 2} known from optical studies of 21P/GZ. For CH{sub 3}OH, we applied our recently published quantum model for the {nu}{sub 3} band to obtain a rotational temperature (48{sup +10}/{sub -7} K) consistent with that obtained for H{sub 2}O. In addition, we developed a new empirical model for the CH{sub 3}OH {nu}{sub 2} band, based on observations of Comet 8P/Tuttle with NIRSPEC. The application of our {nu}{sub 2} model to 21P/GZ yielded a production rate in agreement with that obtained from the {nu}{sub 3} band. Combining results from both {nu}{sub 2} and {nu}{sub 3} bands provided a production rate (47.5 {+-} 4.4 Multiplication-Sign 10{sup 25} s{sup -1}) that corresponded to an abundance ratio of 1.22 {+-} 0.11 Multiplication-Sign 10{sup -2} relative to H{sub 2}O in 21P/GZ, indicating mild depletion of CH{sub 3}OH. Together with observations of 21P/GZ in

Dielectric properties and phase transitions of the piperazinium tetrafluoroborate ([NH{sub 2}(CH{sub 2}){sub 4}NH][BF{sub 4}], abbreviated as PFB) crystal are related to the one-dimensional arrangement of the cations linked by the bistable NH{sup +} Midline-Horizontal-Ellipsis N hydrogen bonds and molecular motions of the [BF{sub 4}]{sup -} units. The crystal structure of [NH{sub 2}(CH{sub 2}){sub 4}NH][BF{sub 4}] is monoclinic at room temperature with the polar space group Pn. The polar/acentric properties of the room temperature phase IV have been confirmed by the piezoelectric and pyroelectric measurements. DSC measurements show that the compound undergoes three first-order structural phase transitions: at 421/411 K (heating/cooling), at 386/372 K and at 364/349 K. {sup 1}H and {sup 19}F NMR measurements indicate the reorientational motions of [BF{sub 4}]{sup -} anions and piperazinium(+) cations as well as the proton motion in the hydrogen-bonded chains of piperazine along the [001] direction. Over the phase I the isotropic reorientational motions or even self-diffusion of the cations and anions are expected. The conductivity measurements in the vicinity of the II-I PT indicate a superionic phase over the phase I. - Graphical abstract: It must be emphasized that the titled compound represents the first organic-inorganic simple salt containing the single-protonated piperazinium cation which was studied by means of the wide variety of experimental techniques. A survey of Cambridge Structural Database (CSD version 5.32 (November 2010) and updates (May 2011)) for structure containing the piperazinium cations yields 248 compounds with the doubly protonated piperazinium(2+) cations and only eight compounds with the singly protonated piperazinium(+) cations. Among these structures only one is the hybrid organic-inorganic material. This is piperazinium nitrate characterized structurally. The crystal packing of [NH{sub 2}(CH{sub 2}){sub 4}NH][BF{sub 4}], phase IV. The

The large photocurrent hysteresis observed in many organometal trihalide perovskite solar cells has become a major hindrance impairing the ultimate performance and stability of these devices, while its origin was unknown. Here we demonstrate the trap states on the surface and grain boundaries of the perovskite materials to be the origin of photocurrent hysteresis and that the fullerene layers deposited on perovskites can effectively passivate these charge trap states and eliminate the notorious photocurrent hysteresis. Fullerenes deposited on the top of the perovskites reduce the trap density by two orders of magnitude and double the power conversion efficiency of CH3NH3PbI3 solar cells. As a result, the elucidation of the origin of photocurrent hysteresis and its elimination by trap passivation in perovskite solar cells provides important directions for future enhancements to device efficiency.

The Waste Isolation Pilot Plant (WIPP) Transuranic Waste Baseline Inventory Report (WTWBIR) establishes a methodology for grouping wastes of similar physical and chemical properties, from across the US Department of Energy (DOE) transuranic (TRU) waste system, into a series of ``waste profiles`` that can be used as the basis for waste form discussions with regulatory agencies. The majority of this document reports TRU waste inventories of DOE defense sites. An appendix is included which provides estimates of commercial TRU waste from the West Valley Demonstration Project. The WIPP baseline inventory is estimated using waste streams identified by the DOE TRU waste generator/storage sites, supplemented by information from the Mixed Waste Inventory Report (MWIR) and the 1994 Integrated Data Base (IDB). The sites provided and/or authorized all information in the Waste Stream Profiles except the EPA (hazardous waste) codes for the mixed inventories. These codes were taken from the MWIR (if a WTWBIR mixed waste stream was not in MWIR, the sites were consulted). The IDB was used to generate the WIPP radionuclide inventory. Each waste stream is defined in a waste stream profile and has been assigned a waste matrix code (WMC) by the DOE TRU waste generator/storage site. Waste stream profiles with WMCs that have similar physical and chemical properties can be combined into a waste matrix code group (WMCG), which is then documented in a site-specific waste profile for each TRU waste generator/storage site that contains waste streams in that particular WMCG.

This report consists of the waste stream profile for the WIPP transuranic waste baseline inventory at Lawrence Livermore National Laboratory. The following assumptions/modifications were made by the WTWBIR team in developing the LL waste stream profiles: since only current volumes were provided by LL, the final form volumes were assumed to be the same as the current volumes; the WTWBIR team had to assign identification numbers (IDs) to those LL waste streams not given an identifier by the site, the assigned identification numbers are consistent with the site reported numbers; LL Final Waste Form Groups were modified to be consistent with the nomenclature used in the WTWBID, these changes included word and spelling changes, the assigned Final Waste Form Groups are consistent with the information provided by LL; the volumes for the year 1993 were changed from an annual rate of generation (m{sup 3}/year) to a cumulative value (m{sup 3}).

The rotational distributions of CO products from the dissociation of ketene at photolysis energies 10 cm{sup {minus}1} below, 56, 110, 200, 325, 425, 1,107, 1,435, 1,720, and 2,500 cm{sup {minus}1} above the singlet threshold, are measured in a supersonic free jet of ketene. The CO(v{double_prime} = 0) rotational distributions at 56, 110, 200, 325, and 425 cm{sup {minus}1} are bimodal. The peaks at low J`s, which are due to CO from the singlet channel, show that the product rotational distribution of CO product from ketene dissociation on the singlet surface is well described by phase space theory (PST). For CO(v{double_prime} = 0) rotational distributions at higher excess energies, the singlet and triplet contributions are not clearly resolved, and the singlet/triplet branching ratios are estimated by assuming that PST accurately predicts the CO rotational distribution from the singlet channel and that the distribution from the triplet channel changes little from that at 10 cm{sup {minus}1} below the singlet threshold. At 2,500 cm{sup {minus}1} excess energy, the CO(v{double_prime} = 1) rotational distribution is obtained, and the ratio of CO(v{double_prime} = 1) to CO(v{double_prime} = 0) products for the singlet channel is close to the variational RRKM calculation, 0.038, and the separate statistical ensembles (SSE) prediction, 0.041, but much greater than the PST prediction, 0.016. Rate constants for the dissociation of ketene (CH{sub 2}CO) and deuterated ketene (CD{sub 2}CO) have been measured at the threshold for the production of the CH(D){sub 2} and CO. Sharp peaks observed in photofragment excitation (PHOFEX) spectra probing CO (v = 0, J = 2) product are identified with the C-C-O bending mode of the transition state. RRKM calculations are carried out for two limiting cases for the dynamics of K-mixing in highly vibrationally excited reactant states.

A second form of the literature-known layered weak ferromagnet Fe[(CH{sub 3}PO{sub 3})(H{sub 2}O)] has been isolated. The crystal structure determination of this new form (2) has been carried out at T=300, 200 and 130K. It crystallizes in the orthorhombic space group Pmn2{sub 1}: a=5.7177(11), b=8.8093(18), c=4.8154(10)A, while form (1) crystallizes in the space group Pna2{sub 1}: a=17.58(2), b=4.814(1), c=5.719(1)A. Moessbauer spectroscopy on form (2) has been performed in the temperature range 4-300K; and, at T{approx}160K, a drastic change in the quadrupole splitting ({delta}E) and a broadening of the doublet components is noticed. But surprisingly, on cooling the crystal, no structural change is observed, which could account for the increase in {delta}E. Below T=25K, {sup 57}Fe spectra transform into hyperfine splitting patterns which reveal a magnetically ordered state in agreement with the results of earlier magnetic susceptibility studies.

We report an 11.4%-efficient perovskite CH{sub 3}NH{sub 3}PbI{sub 3} solar cell using low-cost molybdenum oxide/aluminum (i.e., MoO{sub x}/Al) as an alternative top contact to replace noble/precious metals (e.g., Au or Ag) for extracting photogenerated holes. The device performance of perovskite solar cells using a MoO{sub x}/Al top contact is comparable to that of cells using the standard Ag top contact. Analysis of impedance spectroscopy measurements suggests that using 10-nm-thick MoO{sub x} and Al does not affect charge-recombination properties of perovskite solar cells. Using a thicker (20-nm) MoO{sub x} layer leads to a lower cell performance caused mainly by a reduced fill factor. Our results suggest that MoO{sub x}/Al is promising as a low-cost and effective hole-extraction contact for perovskite solar cells.

The formation of ketene (H{sub 2}CCO) in methane-carbon monoxide (CH{sub 4}-CO) ices was investigated upon its exposure to ionizing radiation in the form of energetic electrons at 5.5 K. The radiation-induced nonthermal equilibrium processing of these ices was monitored online and in situ via infrared spectroscopy complimented with post-irradiation temperature programmed desorption studies exploiting highly sensitive reflectron time-of-flight mass spectrometry (ReTOF) coupled with single photon fragment-free photo ionization (PI) at 10.49 eV. The detection of ketene in irradiated (isotopically labeled) methane-carbon monoxide ices was confirmed via the ?{sub 2} infrared absorption band and substantiated during the warm-up phase based on sublimation profiles obtained from the ReTOF-PI spectra of the corresponding isotopic masses. The experiments conducted with the mixed isotopic ices of {sup 12}CD{sub 4}-{sup 13}CO provide clear evidence of the formation of at least two ketene isotopomers (D{sub 2} {sup 12}C{sup 13}CO and D{sub 2} {sup 13}C{sup 13}CO), allowing for the derivation of two competing formation pathways. We have also proposed underlying reaction mechanisms to the formation of ketene based on kinetic fitting of the temporal evolution of the ketene isotopomers.

Highlights: Black-Right-Pointing-Pointer Comparison of the isotope and mass balance approaches to evaluate the level of methane oxidation within a landfill. Black-Right-Pointing-Pointer The level of methane oxidation is not homogenous under the landfill cover and is strongly correlated to the methane flux. Black-Right-Pointing-Pointer Isotope tracking of the contribution of the methane oxidation to the CO{sub 2} concentrations in the ambient air. - Abstract: We are presenting here a multi-isotope approach ({delta}{sup 13}C and {delta}{sup 18}O of CO{sub 2}; {delta}{sup 13}C and {delta}D of CH{sub 4}) to assess (i) the level(s) of methane oxidation during waste biodegradation and its migration through a landfill cover in Sonzay (France), and (ii) its contribution to the atmospheric CO{sub 2} levels above the surface. The isotope approach is compared to the more conventional mass balance approach. Results from the two techniques are comparable and show that the CH{sub 4} oxidation under the landfill cover is heterogenous, with low oxidation percentages in samples showing high biogas fluxes, which was expected in clay covers presenting fissures, through which CH{sub 4} is rapidly transported. At shallow depth, more immobile biogas pockets show a higher level of CH{sub 4} oxidation by the methanotrophic bacteria. {delta}{sup 13}C of CO{sub 2} samples taken at different heights (from below the cover up to 8 m above the ground level) were also used to identify and assess the relative contributions of its main sources both under the landfill cover and in the surrounding atmosphere.

Our search for new organic superconductors has led us to explore the suitability of large polyfluorinated anions, in analogy to these perfluorinated organometallic complex anions. In this paper, we report the discovery of superconductivity (diamagnetic onset transition temperature of 5.2 K) at ambient pressure in {beta}-(ET){sub 2}SF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3}, along with the synthesis and the crystal and band electronic structures of this novel salt. Small single crystals of the title compound were synthesized by the electrocrystallization method, with the use of a mixture of LiSF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3} and 12-crown-4 in 1,1,2-trichloroethane as a electrolyte. An initial current density of 0.20 {mu}A/cm{sup 2} was applied through the platinum wire electrodes and then increased to 0.41 {mu}A/cm{sup 2} after 1 week, at which point crystallization commenced. The crystal growth was continued for 35 days. Inferior crystals of the same composition and crystal structure, but with lower T{sub c} values, were formed when tetrdydrofuran was used as a solvent. {beta}-(ET){sub 2}SF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3} is the first example of an organic superconductor where not only the radical cation but also the charge-compensating anion consists of an organic molecule. The vast majority of organic superconductors contain diamagnetic metal complex anions, while the remainder of the previously reported superconducting salts contain small inorganic anions such as polyhalides. 20 refs., 2 figs.

Here we have performed inelastic neutron scattering (INS) experiments to investigate the magnetic excitations in the weakly distorted face-centered-cubic (fcc) iridate double perovskites Lamore¬†¬Ľ $_2$ZnIrO$_6$ and La$_2$MgIrO$_6$, which are characterized by A-type antiferromagnetic ground states. The powder inelastic neutron scattering data on these geometrically frustrated $$j_{\\rm eff}=1/2$$ Mott insulators provide clear evidence for gapped spin wave excitations with very weak dispersion. The INS results and thermodynamic data on these materials can be reproduced by conventional Heisenberg-Ising models with significant uniaxial Ising anisotropy and sizeable second-neighbor ferromagnetic interactions. Such a uniaxial Ising exchange interaction is symmetry-forbidden on the ideal fcc lattice, so that it can only arise from the weak crystal distortions away from the ideal fcc limit. This may suggest that even weak distortions in $$j_{\\rm eff}=1/2$$ Mott insulators might lead to strong exchange anisotropies. More tantalizingly, however, we find an alternative viable explanation of the INS results in terms of spin models with a dominant Kitaev interaction. In contrast to the uniaxial Ising exchange, the highly-directional Kitaev interaction is a type of exchange anisotropy which is symmetry-allowed even on the ideal fcc lattice. The Kitaev model has a magnon gap induced by quantum order-by-disorder, while weak anisotropies of the Kitaev couplings generated by the symmetry-lowering due to lattice distortions can pin the order and enhance the magnon gap. In conclusion, our findings highlight how even conventional magnetic orders in heavy transition metal oxides may be driven by highly-directional exchange interactions rooted in strong spin-orbit coupling.¬ę¬†less

Ni/Al{sub 2}O{sub 3} catalyst promoted by Co and ZrO{sub 2} was prepared by co-impregnation method and treated with glow discharge plasma. The catalytic activity of the synthesized nanocatalysts has been tested toward conversion of CH{sub 4}/CO{sub 2} to syngas. The physicochemical characterizations like XRD, EDX, FESEM, TEM, BET, FTIR, and XPS show that plasma treatment results in smaller particle size, more surface concentration, and uniform morphology. The dispersion of nickel in plasma-treated nanocatalyst was also significantly improved, which was helpful for controlling the ensemble size of active phase atoms on the support surface. Improved physicochemical properties caused 20%‚Äď30% enhancement in activity of plasma-treated nanocatalyst that means to achieve the same H{sub 2} or CO yield, the plasma-treated nanocatalyst needed about 100 ¬įC lower reaction temperature. The H{sub 2}/CO ratio got closer to 1 at higher temperatures and finally at 850 ¬įC H{sub 2}/CO = 1 is attained for plasma-treated nanocatalyst. Plasma-treated nanocatalyst due to smaller Ni particles and strong interaction between active phase and support has lower tendency to keep carbon species on its structure and hence excellent stability can be observed for this catalyst.

Co/sub 3/(CO)/sub 9/CCH/sub 2/C(CH/sub 3/)/sub 3/ reacted with hydrogen in aromatic solvents to yield 3,3-dimethylbutene, 2,2-dimethylbutane, and 4,4-dimethylpentanal. First order decomposition of starting material and a hydrogen pressure dependence for the rate of appearance of total products were indicated. The hydrogenation was inhibited in the presence of carbon monoxide (CO:H/sub 2/, 3.7:3.7 atm, 60/sup 0/C), but at 85/sup 0/ under the same CO/H/sub 2/ atmosphere, aldehyde production became the predominant reaction pathway at the expense of earlier-formed olefin. Incorporation of independently added olefins in the hydrogenation suggested the intermediacy of olefin aldehyde ad alkane production. A polystyrene-attached n/sup 5/-cyclopentadienyl(tricarbonyl)-hydridomolybdenum complex was prepared and its reactions with several THF-soluble bases were investigated. Enolates of ..beta..-dicarbonyl compounds quantitatively deprotonated this complex, giving polymer-bound salts of the corresponding anion. Little change in pKa in THF was induced by binding the molybdenum hydride to the polymer. Even though the polymer-supported partners rendered the reactions heterogeneous, the systems adhered reasonably well to conventional equilibrium behavior. A polymer-bound carboxylic acid and its conjugate base also displayed essentially conventional equilibrium dynamics.

The present invention is the addition of a semiconductor material and energy to the reaction mixture of organic, acid (for example, trifluoroacetate), and oxygen. A transition metal ion may be added to the reaction mixture. The semiconductor material converts energy to oxidants thereby promoting oxidation of the organic. Alternatively, using metal in combination with exposure to light may be used.

The present invention is the addition of a semiconductor material and energy to the reaction mixture of organic, acid (for example, trifluoroacetate), and oxygen. A transition metal ion may be added to the reaction mixture. The semiconductor material converts energy to oxidants thereby promoting oxidation of the organic. Alternatively, using metal in combination with exposure to light may be used.

Ab initio, multireference, configuration interaction (CI) calculations have been used to characterize the ground-state potential surface of methylene. The calculations employ a full-valence complete-active-space reference wave function and a (4s,3p,2d,If/3s,2p,1d) basis set. The calculations were carried out at approximately 6000 points, and the resulting energies were fit to a many-body expansion including conical intersections between the [sup 3]B[sub 1] and [sup 3]A[sub 2] states for C[sub 2v] geometries and between the [sup 3]II and [sup 3][Sigma][sup [minus

Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe){sub 2}]{sub 2} and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.

The year 2008 resulted in 99 scans that were funded through NIH agencies. An additional 43 MRI scans were funded by industry. Over 250 scans were acquired by various investigators as ÔŅĹpilotÔŅĹ data to be used for future grant applications. While these numbers are modest in comparison to most busy research MRI Centers, they are in line with that of a newly established MRI research facility. The initial 12-18 months of operation were primarily dedicated to establishing new IRB approved research studies, and acquiring pilot data for future grant applications. During the year 2009 the MRI Center continued to show positive growth with respect to funded studies and the number of scan sessions. The number of NIH sponsored scans increased to 242 and the number of industry funded studies climbed to 81. This more than doubled our numbers of funded scans over the previous year. In addition, 398 scans were acquired as pilot data; most of which were fMRIÔŅĹs. The MRI Center continued to expand with additional researchers who were interested in probing the brainÔŅĹs response to chronic pain. Other studies looked at regions of brain activation in patients with impulsivity disorders; including smokers. A large majority of the imaging studies were focused on the brain; however, the MRI Center continued to accommodate the needs of various types of investigators, who studied various types of human pathology. Studies of porcine cardiac function and myocardial perfusion were performed. Another study of ultra-fast acute abdominal MRI in children was underway; eventually leading to publication in AJR. These non-neuro type research projects allowed the MRI Center to expand upon the depth and breadth of service that has now become available to researchers at UVM. The UVM MRI Center became the first clinical/research site in North America to install dual radio frequency (RF) amplifiers on a 3T MRI system. The use of dual RF amplifiers helps to eliminate standing wave artifacts that are prevalent at 3T. Standing wave artifacts often rendered spine or abdominal 3T MR images to be poor quality or unreadable prior to the availability of multi-transmit. A research collaboration agreement with Philips Healthcare, Best, Netherlands allowed our site to have first use of the technology; while at the same time giving us the opportunity to provide critical feedback to Philips Healthcare about our experiences with multi-transmit. This dramatically improved image quality for 3T MRI sites across the US and the world. Philips has stationed an onsite MRI physicist at UVM to work collaboratively with researchers at the University of Vermont on various MRI related projects. He has worked collaboratively with UVM investigators toward the design and publication of several journal articles and abstracts during his time at UVM. As the MRI Center advanced through the year 2010, an additional MRI technologist and a MRI physicist were hired to accommodate the increased demand for MRI scanning and data processing expertise. This enabled us to not only expand our hours of operation; it also helped to augment our MRI pulse programming and data processing capabilities. Studies that used state-of-the-art MRI techniques like pseudo continuous arterial spin labeling (pCASL) allowed researchers from the Department of Obstetrics and Reproductive Services to obtain non-contrast brain perfusion values of women to help them to better understand the effects of preeclampsia. At year-end 2010 the MRI Center completed 303 NIH funded and 198 industry funded scans. The number of no charge pilot scans decreased to 189.

A major yet unresolved quest in decoding the human genome is the identification of the regulatory sequences that control the spatial and temporal expression of genes. Distant-acting transcriptional enhancers are particularly challenging to uncover since they are scattered amongst the vast non-coding portion of the genome. Evolutionary sequence constraint can facilitate the discovery of enhancers, but fails to predict when and where they are active in vivo. Here, we performed chromatin immunoprecipitation with the enhancer-associated protein p300, followed by massively-parallel sequencing, to map several thousand in vivo binding sites of p300 in mouse embryonic forebrain, midbrain, and limb tissue. We tested 86 of these sequences in a transgenic mouse assay, which in nearly all cases revealed reproducible enhancer activity in those tissues predicted by p300 binding. Our results indicate that in vivo mapping of p300 binding is a highly accurate means for identifying enhancers and their associated activities and suggest that such datasets will be useful to study the role of tissue-specific enhancers in human biology and disease on a genome-wide scale.

Management Program - March 2014 | Department of Energy Review, Bonneville Power Administration Safety Management Program - March 2014 Independent Oversight Review, Bonneville Power Administration Safety Management Program - March 2014 March 2014 Oversight Review of the Bonneville Power Administration Safety Management Program Bonneville Power Administration management requested that the U.S. Department of Energy Office of Enforcement and Oversight (Independent Oversight), within the Office

Self- and nitrogen-broadened line shape data for the Pe(11) line of the ?? + ?? band of acetylene, recorded using a frequency comb-stabilized laser spectrometer, have been analyzed using the HartmannĖTran profile (HTP) line shape model in a multispectrum fitting. In total, the data included measurements recorded at temperatures between 125 K and 296 K and at pressures between 4 and 760 Torr. New, sub-Doppler, frequency comb-referenced measurements of the positions of multiple underlying hot band lines have also been made. These underlying lines significantly affect the Pe(11) line profile at temperatures above 240 K and poorly known frequencies previouslymore†Ľintroduced errors into the line shape analyses. The behavior of the HTP model was compared to the quadratic speed dependent Voigt profile (QSDVP) expressed in the frequency and time domains. A parameter uncertainty analysis was carried out using a Monte Carlo method based on the estimated pressure, transmittance and frequency measurement errors. From the analyses, the Pe(11) line strength was estimated to be 1.2014(50) ◊ 10-20 in cm.molecules?Ļ units at 296 K with the standard deviation in parenthesis. For analyzing these data, we found that a reduced form of the HTP, equivalent to the QSDVP, was most appropriate because the additional parameters included in the full HTP were not well determined. As a supplement to this work, expressions for analytic derivatives and a lineshape fitting code written in Matlab for the HTP are available.ę†less

Low quality natural gas processing with the integrated CFZ/CNG Claus process is feasible for low quality natural gas containing 10% or more of CO{sub 2}, and any amount of H{sub 2}S. The CNG Claus process requires a minimum CO{sub 2} partial pressure in the feed gas of about 100 psia (15% CO{sub 2} for a 700 psia feed gas) and also can handle any amount of H{sub 2}S. The process is well suited for handling a variety of trace contaminants usually associated with low quality natural gas and Claus sulfur recovery. The integrated process can produce high pressure carbon dioxide at purities required by end use markets, including food grade CO{sub 2}. The ability to economically co-produce high pressure CO{sub 2} as a commodity with significant revenue potential frees process economic viability from total reliance on pipeline gas, and extends the range of process applicability to low quality gases with relatively low methane content. Gases with high acid gas content and high CO{sub 2} to H{sub 2}S ratios can be economically processed by the CFZ/CNG Claus and CNG Claus processes. The large energy requirements for regeneration make chemical solvent processing prohibitive. The cost of Selexol physical solvent processing of the LaBarge gas is significantly greater than the CNG/CNG Claus and CNG Claus processes.

The mode-selective chemistry of the title reaction is studied by full-dimensional quantum dynamics simulation on an accurate ab initio potential energy surface for vanishing total angular momentum. Using a rigorous transition state based approach and multi-configurational time-dependent Hartree wave packet propagation, initial state-selected reaction probabilities for many ro-vibrational states of methane are calculated. The theoretical results are compared with experimental trends seen in reactions of methane. An intuitive interpretation of the ro-vibrational control of the chemical reactivity provided by a sudden model based on the quantum transition state concept is discussed.

The dynamics of the hydrogen abstraction reaction between methane and hydroxyl radical is investigated using an initial state selected time-dependent wave packet method within a six-dimensional model. The ab initio calibrated global potential energy surface of Espinosa-GarcŪa and Corchado was used. Integral cross sections from several low-lying rotational states of both reactants have been obtained using the centrifugal sudden and J-shifting approximations. On the empirical potential energy surface, the rotational excitation of methane has little effect on the reaction cross section, but excited rotational states of OH inhibit the reactivity slightly. These results are rationalized with the newly proposed sudden vector projection model.

The ring polymer molecular dynamics (RPMD) calculations are performed to calculate rate constants for the title reaction on the recently constructed potential energy surface based on permutation invariant polynomial (PIP) neural-network (NN) fitting [J. Li et al., J. Chem. Phys. 142, 204302 (2015)]. By inspecting convergence, 16 beads are used in computing free-energy barriers at 300‚ÄāK ‚Č§ T ‚Č§ 1000‚ÄāK, while different numbers of beads are used for transmission coefficients. The present RPMD rates are in excellent agreement with quantum rates computed on the same potential energy surface, as well as with the experimental measurements, demonstrating further that the RPMD is capable of producing accurate rates for polyatomic chemical reactions even at rather low temperatures.

The selective capture of radiological iodine (129I) is a persistent concern for safe nuclear energy. In these nuclear fuel reprocessing scenarios, the gas streams to be treated are extremely complex, containing several distinct iodine-containing molecules amongst a large variety of other species. Silver-containing mordenite (MOR) is a longstanding benchmark for radioiodine capture, reacting with molecular iodine (I2) to form AgI. However the mechanisms for organoiodine capture is not well understood. Here we investigate the capture of methyl iodide from complex mixed gas streams by combining chemical analysis of the effluent gas stream with in depth characterization of the recovered sorbent.more¬†¬Ľ Tools applied include infrared spectroscopy, thermogravimetric analysis with mass spectrometry, micro X-ray fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. Moreover, the MOR zeolite catalyzes decomposition of the methyl iodide through formation of surface methoxy species (SMS), which subsequently reacts with water in the mixed gas stream to form methanol, and with methanol to form dimethyl ether, which are both detected downstream in the effluent. The liberated iodine reacts with Ag in the MOR pore to the form subnanometer AgI clusters, smaller than the MOR pores, suggesting that the iodine is both physically and chemically confined within the zeolite.¬ę¬†less

The effective capture and storage of radiological iodine (129I) remains a strong concern for safe nuclear waste storage and safe nuclear energy. Silver-containing mordenite (MOR) is a longstanding benchmark for iodine capture. In nuclear fuel reprocessing scenarios, complex gas streams will be present and the need for high selectivity of all iodine containing compounds is of the utmost importance for safety and the environment. In particular, a molecular level understanding of the sorption of organic iodine compounds is not well understood. Here we probe the structure and distribution of methyl iodide sorbed by silver-containing MOR using a combination of crystallographic and materials characterization techniques including: infrared spectroscopy, thermogravimetric analysis with mass spectrometry, Micro-X-ray Fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. The iodine is captured inside the MOR pore in the form of AgI nanoparticles, that is consistent with the pores sizes of the MOR, indicating that the molecule is both physically and chemically captured in the Ag-MOR. The organic component is surface catalyzed by the zeolite via the formation of Surface Methoxy Species (SMS) that result in downstream organics of dimethyl ether and methanol formation.

In this work, we study the transport of methane in the external water envelopes surrounding water-rich super-Earths. We investigate the influence of methane on the thermodynamics and mechanics of the water mantle. We find that including methane in the water matrix introduces a new phase (filled ice), resulting in hotter planetary interiors. This effect renders the super-ionic and reticulating phases accessible to the lower ice mantle of relatively low-mass planets (‚ąľ5 M{sub E} ) lacking a H/He atmosphere. We model the thermal and structural profile of the planetary crust and discuss five possible crustal regimes which depend on the surface temperature and heat flux. We demonstrate that the planetary crust can be conductive throughout or partly confined to the dissociation curve of methane clathrate hydrate. The formation of methane clathrate in the subsurface is shown to inhibit the formation of a subterranean ocean. This effect results in increased stresses on the lithosphere, making modes of ice plate tectonics possible. The dynamic character of the tectonic plates is analyzed and the ability of this tectonic mode to cool the planet is estimated. The icy tectonic plates are found to be faster than those on a silicate super-Earth. A mid-layer of low viscosity is found to exist between the lithosphere and the lower mantle. Its existence results in a large difference between ice mantle overturn timescales and resurfacing timescales. Resurfacing timescales are found to be 1 Ma for fast plates and 100 Ma for sluggish plates, depending on the viscosity profile and ice mass fraction. Melting beneath spreading centers is required in order to account for the planetary radiogenic heating. The melt fraction is quantified for the various tectonic solutions explored, ranging from a few percent for the fast and thin plates to total melting of the upwelled material for the thick and sluggish plates. Ice mantle dynamics is found to be important for assessing the composition of the atmosphere. We propose a mechanism for methane release into the atmosphere, where freshly exposed reservoirs of methane clathrate hydrate at the ridge dissociate under surface conditions. We formulate the relation between the outgassing flux and the tectonic mode dynamical characteristics. We give numerical estimates for the global outgassing rate of methane into the atmosphere. We find, for example, that for a 2 M{sub E} planet outgassing can release 10{sup 27}-10{sup 29} molecules s{sup ‚Äď1} of methane to the atmosphere. We suggest a qualitative explanation for how the same outgassing mechanism may result in either a stable or a runaway volatile release, depending on the specifics of a given planet. Finally, we integrate the global outgassing rate for a few cases and quantify how the surface atmospheric pressure of methane evolves over time. We find that methane is likely an important constituent of water planets' atmospheres.

A novel electricity-free deposition of palladium on the surface of manganese dioxide, which has a crystal structure of ramsdellite, was studied. Using the Pd deposition, a nano-particle of Pd/MnO2 was prepared, and it was used for a catalytic performance for reforming methane into hydrogen at 300 C.

The selective capture of radiological iodine (129I) is a persistent concern for safe nuclear energy. In these nuclear fuel reprocessing scenarios, the gas streams to be treated are extremely complex, containing several distinct iodine-containing molecules amongst a large variety of other species. Silver-containing mordenite (MOR) is a longstanding benchmark for radioiodine capture, reacting with molecular iodine (I2) to form AgI. However the mechanisms for organoiodine capture is not well understood. Here we investigate the capture of methyl iodide from complex mixed gas streams by combining chemical analysis of the effluent gas stream with in depth characterization of the recovered sorbent. Tools applied include infrared spectroscopy, thermogravimetric analysis with mass spectrometry, micro X-ray fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. Moreover, the MOR zeolite catalyzes decomposition of the methyl iodide through formation of surface methoxy species (SMS), which subsequently reacts with water in the mixed gas stream to form methanol, and with methanol to form dimethyl ether, which are both detected downstream in the effluent. The liberated iodine reacts with Ag in the MOR pore to the form subnanometer AgI clusters, smaller than the MOR pores, suggesting that the iodine is both physically and chemically confined within the zeolite.

Both ceria (CeO{sub 2}) and alumina (Al{sub 2}O{sub 3}) are very important catalyst support materials. Neutral binary oxide nanoclusters (NBONCs), Ce{sub x}Al{sub y}O{sub z}, are generated and detected in the gas phase and their reactivity with carbon monoxide (CO) and butane (C{sub 4}H{sub 10}) is studied. The very active species CeAlO{sub 4}{sup ē} can react with CO and butane via O atom transfer (OAT) and H atom transfer (HAT), respectively. Other Ce{sub x}Al{sub y}O{sub z} NBONCs do not show reactivities toward CO and C{sub 4}H{sub 10}. The structures, as well as the reactivities, of Ce{sub x}Al{sub y}O{sub z} NBONCs are studied theoretically employing density functional theory (DFT) calculations. The ground state CeAlO{sub 4}{sup ē} NBONC possesses a kite-shaped structure with an O{sub t}CeO{sub b}O{sub b}AlO{sub t} configuration (O{sub t}, terminal oxygen; O{sub b}, bridging oxygen). An unpaired electron is localized on the O{sub t} atom of the AlO{sub t} moiety rather than the CeO{sub t} moiety: this O{sub t} centered radical moiety plays a very important role for the reactivity of the CeAlO{sub 4}{sup ē} NBONC. The reactivities of Ce{sub 2}O{sub 4}, CeAlO{sub 4}{sup ē}, and Al{sub 2}O{sub 4} toward CO are compared, emphasizing the importance of a spin-localized terminal oxygen for these reactions. Intramolecular charge distributions do not appear to play a role in the reactivities of these neutral clusters, but could be important for charged isoelectronic BONCs. DFT studies show that the reaction of CeAlO{sub 4}{sup ē} with C{sub 4}H{sub 10} to form the CeAlO{sub 4}HēC{sub 4}H{sub 9}{sup ē} encounter complex is barrierless. While HAT processes have been previously characterized for cationic and anionic oxide clusters, the reported study is the first observation of a HAT process supported by a ground state neutral oxide cluster. Mechanisms for catalytic oxidation of CO over surfaces of Al{sub x}O{sub y}/M{sub m}O{sub n} or M{sub m}O{sub n}/Al{sub x}O{sub y} materials are proposed consistent with the presented experimental and theoretical results.

The first synthesis of gracilioether F, a polyketide natural product with an unusual tricyclic core and five contiguous stereocenters, is described. Key steps of the synthesis include a Lewis acid promoted keteneĖalkene [2+2] cycloaddition and a late-stage carboxylic acid directed C(sp≥)óH oxidation. The synthesis requires only eight steps from norbornadiene.

Much of our work during this grant period has emphasized green chemistry and sustainability. For example, we were able to convert glycerine, a waste byproduct of biodiesel production, into lactic acid, a compound with numerous applications, notably in the food and cosmetics industry, as well as being a source material for a biodegradable plastic. This work required a catalyst, that ceases to work after a certain lapse of time. We were able to identify the way in which this deactivation occurs by identifying some of the metal catalyst deactivation products. These proved to be multimetallic clusters containing up to six metals and up to 14 hydrogen atoms. Both the catalytic reaction itself and the deactivation structures are novel and unexpected. We have previously proposed that nitrogen heterocycles could be good energy carriers in a low CO2 future world. In another part of our study, we found catalysts for introduction of hydrogen, an energy carrier that is hard to store, into nitrogen heterocycles. The mechanism of this process proved to be unusual in that the catalyst transfers the H2 to the heterocycle in the form of H+ and H-, first transferring the H+ and only then the H-. In a third area of study, some of our compounds, originally prepared for DOE catalysis purposes, also proved useful in hydrocarbon oxidation and in water oxidation. The latter is important in solar-to-fuel work, because, by analogy with natural photosynthesis, the goal of the Yale Solar Group of four PIs is to convert sunlight to hydrogen and oxygen, which requires water splitting catalysts. The catalysts that proved useful mediate the latter reaction: water oxidation to oxygen. In a more technical study, we developed methods for distinguishing the case where catalysis is mediated by a soluble catalyst from cases where catalysis arises from a deposit of finely divided solid. One particular application involved electrocatalysis, where catalysis is driven by application of a voltage to electrodes dipped in the reactant mixture. We measured the mass increase of an electrode as material is deposited, and were able to see how this process is affected by the voltage supplied to the electrode. Our work continues to be well cited and we often receive requests for information or samples from fellow researchers.

BiOI can be used for photocatalytic reduction of CO{sub 2} into hydrocarbon fuels under sunlight. - Highlights: ē Room temperature synthesis of BiOI flowerlike hierarchical structures. ē BiOI can be used for photocatalytic reduction of CO{sub 2} into hydrocarbon fuels under sunlight. ē The photocatalytic activity of BiOI is higher than that of P25 TiO{sub 2}. - Abstract: BiOI flowerlike hierarchical structure was synthesized by the direct hydrolysis method Ė hydrolysis at room temperature in the presence of polyvinyl pyrrolidone. As-synthesized BiOI was characterized by powder X-ray diffraction, UVĖvis diffuse reflectance spectra, X-ray photoelectron spectroscopy spectra, scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. It is a facile way to obtain BiOI flowerlike hierarchical structure photocatalyst for photocatalytic reduction of CO{sub 2} into hydrocarbon fuels under simulated sunlight irradiation without cocatalyst. And the photocatalytic activity of as-synthesized BiOI is higher than that of P25 TiO{sub 2} and bulk BiOI.

Recently, the efficiency of organolead trihalide perovskite solar cells has improved greatly because of improved material qualities with longer carrier diffusion lengths. Mixing chlorine in the precursor for mixed halide films has been reported to dramatically enhance the diffusion lengths of mixed halide perovskite films, mainly as a result of a much longer carrier recombination lifetime. Here we report that adding Cl containing precursor for mixed halide perovskite formation can induce the abnormal grain growth behavior that yields well-oriented grains accompanied by the appearance of some very large size grains. The abnormal grain growth becomes prominent only after multi-cycle coatingmore¬†¬Ľ of MAI : MACl blend precursor. The large grain size is found mainly to contribute to a longer carrier charge recombination lifetime, and thus increases the device efficiency to 18.9%, but without significantly impacting the carrier transport property. As a result, the strong correlation identified between material process and morphology provides guidelines for future material optimization and device efficiency enhancement.¬ę¬†less

2016 Collegiate Wind Competition | Department of Energy Wind Program Announces New Round of Funding for 2016 Collegiate Wind Competition U.S. Department of Energy Wind Program Announces New Round of Funding for 2016 Collegiate Wind Competition October 30, 2014 - 5:30pm Addthis The U.S. Department of Energy's (DOE's) National Renewable Energy Laboratory today issued a Request for Proposals seeking teams of students to participate in the 2016 U.S. Department of Energy Collegiate Wind

We present a second epoch of observations of the 44 GHz Class I methanol maser line toward the star-forming region Orion Molecular Cloud 2. The observations were carried out with the Very Large Array, and constitute one of the first successful Zeeman effect detections with the new Wide-band Digital Architecture correlator. Comparing to the result of our earlier epoch of data for this region, we find that the intensity of the maser increased by 50%, but the magnetic field value has stayed the same, within the errors. This suggests that the methanol maser may be tracing the large-scale magnetic field that is not affected by the bulk gas motions or turbulence on smaller scales that is causing the change in maser intensity.

IIEC, a division of CERF, has developed an extensive base of experience implementing activities that support climate action by developing USIJI projects in transitional countries within Asia, Latin America, Central and Eastern Europe, and southern Africa. IIEC has been able to provide a range of technical and policy assistance to governments and industry in support of sustainable energy use. IIEC continues to work in key countries with local partners to develop and implement energy efficiency policies and standards, develop site-specific projects, and assist governing bodies to establish national priorities and evaluation criteria for approving GHG-mitigation projects. As part of this project, IIEC focused on promoting a series of activities in Thailand and South Africa in order to identify GHG mitigation projects and work within the national approval process of those countries. The sections of this report outline the activities conducted in each country in order to achieve that goal.

Coherent anti-Stokes Raman scattering (CARS) spectroscopy is used to determine the parameters of gaseous combustion products of hydrogen and hydrocarbon fuels with oxygen at high temperatures and pressures. The methodical aspects of CARS thermometry, which are related to the optimal choice of molecules (diagnostic references) and specific features of their spectra, dependent on temperature and pressure, are analysed. Burning is modelled under the conditions similar to those of real spacecraft propulsion systems using a specially designed laboratory combustion chamber, operating in the pulse-periodic regime at high temperatures (to 3500 K) and pressures (to 20 MPa) of combustion products. (nonlinear optical phenomena)

Recently, the efficiency of organolead trihalide perovskite solar cells has improved greatly because of improved material qualities with longer carrier diffusion lengths. Mixing chlorine in the precursor for mixed halide films has been reported to dramatically enhance the diffusion lengths of mixed halide perovskite films, mainly as a result of a much longer carrier recombination lifetime. Here we report that adding Cl containing precursor for mixed halide perovskite formation can induce the abnormal grain growth behavior that yields well-oriented grains accompanied by the appearance of some very large size grains. The abnormal grain growth becomes prominent only after multi-cycle coating of MAI : MACl blend precursor. The large grain size is found mainly to contribute to a longer carrier charge recombination lifetime, and thus increases the device efficiency to 18.9%, but without significantly impacting the carrier transport property. As a result, the strong correlation identified between material process and morphology provides guidelines for future material optimization and device efficiency enhancement.

This report contains the Appendices for the Analysis of Accident Sequences and Source Terms at Waste Treatment and Storage Facilities for Waste Generated by the U.S. Department of Energy Waste Management Operations. The main report documents the methodology, computational framework, and results of facility accident analyses performed as a part of the U.S. Department of Energy (DOE) Waste Management Programmatic Environmental Impact Statement (WM PEIS). The accident sequences potentially important to human health risk are specified, their frequencies are assessed, and the resultant radiological and chemical source terms are evaluated. A personal computer-based computational framework and database have been developed that provide these results as input to the WM PEIS for calculation of human health risk impacts. This report summarizes the accident analyses and aggregates the key results for each of the waste streams. Source terms are estimated and results are presented for each of the major DOE sites and facilities by WM PEIS alternative for each waste stream. The appendices identify the potential atmospheric release of each toxic chemical or radionuclide for each accident scenario studied. They also provide discussion of specific accident analysis data and guidance used or consulted in this report.

Accurate quantum dynamics calculations for the C({sup 1}D) + H{sub 2} reaction are performed using a real wave packet approach with full Coriolis coupling. The newly constructed ZMB-a ab initio potential energy surface [Zhang et al., J. Chem. Phys. 140, 234301 (2014)] is used. The integral cross sections (ICSs), differential cross sections (DCSs), and product state distributions are obtained over a wide range of collision energies. In contrast to previous accurate quantum dynamics calculations on the reproducing kernel Hilbert space potential energy surface, the present total ICS is much larger at low collision energies, yielding larger rate coefficients in better agreement with experiment and with slight inverse temperature dependence. Meanwhile, interesting nonstatistical behaviors in the DCSs are revealed. In particular, the DCSs display strong oscillations with the collision energy; forward biased product angular distribution appears when only small J partial wave contributions are included; alternate forward and backward biases emerge with very small increments of collision energy; and the rotational state-resolved DCSs show strong oscillations with the scattering angle. Nevertheless, the total DCSs can be roughly regarded as backward‚Äďforward symmetric over the whole energy range and are in reasonably good agreement with the available experimental measurements.

An integrated field-laboratory program evaluated the use of radon and CO2 flux measurements to constrain source and timescale of CO2 fluxes in environments proximate to CO2 storage reservoirs. By understanding the type and depth of the gas source, the integrity of a CO2 storage reservoir can be assessed and monitored. The concept is based on correlations of radon and CO2 fluxes observed in volcanic systems. This fundamental research is designed to advance the science of Monitoring, Verification, and Accounting (MVA) and to address the Carbon Storage Program goal of developing and validating technologies to ensure 99 percent storage performance. Graduate and undergraduate students conducted the research under the guidance of the Principal Investigators; in doing so they were provided with training opportunities in skills required for implementing and deploying CCS technologies. Although a final method or ‚Äútool‚ÄĚ was not developed, significant progress was made. The field program identified issues with measuring radon in environments rich in CO2. Laboratory experiments determined a correction factor to apply to radon measurements made in CO2-bearing environments. The field program also identified issues with radon and CO2-flux measurements in soil gases at a natural CO2 analog. A systematic survey of radon and CO2 flux in soil gases at the LaBarge CO2 Field in Southwest Wyoming indicates that measurements of 222Rn (radon), 220Rn (thoron), and CO2 flux may not be a robust method for monitoring the integrity of a CO2 storage reservoir. The field program was also not able to correlate radon and CO2 flux in the CO2-charged springs of the Thermopolis hydrothermal system. However, this part of the program helped to motivate the aforementioned laboratory experiments that determined correction factors for measuring radon in CO2-rich environments. A graduate student earned a Master of Science degree for this part of the field program; she is currently employed with a

From the title, the reader is led to expect a broad practical treatise on combustion and combustion devices. Remarkably, for a book of modest dimension, the author is able to deliver. The text is organized into 12 Chapters, broadly treating three major areas: combustion fundamentals -- introduction (Ch. 1), thermodynamics (Ch. 2), fluid mechanics (Ch. 7), and kinetics (Ch. 8); fuels -- coal, municipal solid waste, and other solid fuels (Ch. 4), liquid (Ch. 5) and gaseous (Ch. 6) fuels; and combustion devices -- fuel cells (Ch. 3), boilers (Ch. 4), Otto (Ch. 10), diesel (Ch. 11), and Wankel (Ch. 10) engines and gas turbines (Ch. 12). Although each topic could warrant a complete text on its own, the author addresses each of these major themes with reasonable thoroughness. Also, the book is well documented with a bibliography, references, a good index, and many helpful tables and appendices. In short, Applied Combustion does admirably fulfill the author`s goal for a wide engineering science introduction to the general subject of combustion.

An acceptor and a single donor state of carbon-hydrogen defects (CH{sub A} and CH{sub B}) are observed by Laplace deep level transient spectroscopy at 90‚ÄČK. CH{sub A} appears directly after hydrogenation by wet chemical etching or hydrogen plasma treatment, whereas CH{sub B} can be observed only after a successive annealing under reverse bias at about 320‚ÄČK. The activation enthalpies of these states are 0.16‚ÄČeV for CH{sub A} and 0.14‚ÄČeV for CH{sub B}. Our results reconcile previous controversial experimental results. We attribute CH{sub A} to the configuration where substitutional carbon binds a hydrogen atom on a bond centered position between carbon and the neighboring silicon and CH{sub B} to another carbon-hydrogen defect.

The C3-C5 peroxyacyl nitrates RC(O)OONO{sub 2} (R=Et, n-Pr, i-Pr, n-Bu, i-Bu, sec-Bu, t-Bu, Ch{sub 2}=CH- and CH{sub 2}=C(CH{sub 3})-) have been synthesized and prepared in situ and have been characterized by electron capture gas chromatography. Their thermal decomposition rates have been measured and are similar to that of PAN (R = CH{sub 3}). Carbonyl products have been identified and the corresponding reaction mechanisms have been outlined. Ambient levels of several peroxyacyl nitrates (R =CH{sub 3}, Et, n-Pr and CH{sub 2}=(CH{sub 3})-) have been measured. The results are discussed with focus on atmospheric hydrocarbons as precursors to C3-C5 peroxyacyl nitrates in the atmosphere.